Novel cyclopropane carboxylic acid esters

ABSTRACT

Novel cyclopropane carboxylic acid esters of the formula ##STR1## wherein X 1  is selected from the group consisting of hydrogen, fluorine, chlorine and bromine, X 2  is selected from the group consisting of fluorine, chlorine and bromine, X 3  is selected from the group consisting of chlorine, bromine and iodine and R is selected from the group consisting of ##STR2## and benzyl optionally substituted with at least one member of the group consisting of alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkenyloxy of 2 to 6 carbon atoms, alkadienyl of 4 to 8 carbon atoms, methylenedioxy, benzyl and halogens, R 1  is selected from the group consisting of hydrogen and methyl, R 2  is selected from the group consisting of monocyclic aryl and --CH 2  --C.tbd.CH,R 3  is an aliphatic of 2 to 6 carbon atoms having at least one double bond, R 4  is selected from the group consisting of hydrogen, --CN and --C.tbd.CH, R 5  is selected from the group consisting of chlorine and methyl, n is 0, 1 or 2, R 6 , R 7 , R 8 , and R 9  are individually selected from the group consisting of hydrogen, chlorine and methyl and S/I indicates that the ring may be aromatic, dihydro or tetrahydro having pesticidal properties, and a process for their preparation.

PRIOR APPLICATION

This application is a continuation-in-part of our copending, commonlyassigned U.S. patent application Ser. No. 834,659 filed Sept. 19, 1977,now abandoned and Ser. No. 5,375 filed January 22, 1979 now abandoned.

OBJECTS OF THE INVENTION

It is an object of the invention to provide the novel cyclopropanecarboxylic acid esters of formula I and a novel process for theirpreparation.

It is another object of the invention to provide novel pesticidalcompositions containing at least one compound of formula I as the activeingredient.

It is an additional object of the invention to provide a novel processof combatting pests including insects, fungi, acarids, nematodes andticks.

These and other objects and advantages of the invention will becomeobvious from the following detailed description.

THE INVENTION

The novel cyclopropane carboxylic acid esters of the invention have theformula ##STR3## wherein X₁ is selected from the group consisting ofhydrogen, fluorine, chlorine and bromine, X₂ is selected from the groupconsisting of fluorine, chlorine and bromine, X₃ is selected from thegroup consisting of chlorine, bromine and iodine and R is selected fromthe group consisting of ##STR4## and benzyl optionally substituted withat least one member of the group consisting of alkyl of 1 to 4 carbonatoms, alkenyl of 2 to 6 carbon atoms, alkenyloxy of 2 to 6 carbonatoms, alkadienyl of 4 to 8 carbon atoms, methylenedioxy, benzyl andhalogens, R₁ is selected from the group consisting of hydrogen andmethyl, R₂ is selected from the group consisting of monocyclic aryl and--CH₂ --C.tbd.CH,R₃ is an aliphatic of 2 to 6 carbon atoms having atleast one double bond, R₄ is selected from the group consisting ofhydrogen, --CN and --C.tbd.CH, R₅ is selected from the group consistingof chlorine and methyl, n is 0, 1 or 2, R₆, R₇, R₈ and R₉ areindividually selected from the group consisting of hydrogen, chlorineand methyl and S/I indicates that the ring may be aromatic, dihydro ortetrahydro.

Among the preferred groups of formula I, R₂ is 5-benzyl-3-furyl-methyl,R₃ is vinyl, propen-1-yl, buta-1,3-dienyl or buten-1-yl, R₅ is3-phenoxy-benzyl, α-cyano-3-phenoxy-benzoyl orα-ethynyl-3-phenoxy-benzyl. By convention, in the alcohol moiety of theester of formula I when n is 0, the ring which is fixed the R₅substituent is then a benzene ring.

The esters of formula I exist in numerous isomeric forms since thecyclopropane carboxylic acids used to form the esters of formula Igenerally have 3 asymetric carbon atoms, namely the 1- and 3-carbonatoms of the cyclopropane ring and the 1'-carbon atom of polyhalogenatedethyl fixed in the 3-position of the cyclopropane ring. When the threeX₁, X₂ and X₃ substituents are all different from each other, anadditional asymetric carbon atom exists in the 2'-position of the3-polyhalogenated ethyl group. Moreover, the alcohol moiety of theesters of formula I may also contain one or more asymetric carbon atomsand/or one or more double bonds making E or Z isomers. The esters offormula I include within their scope any combination of the isomericform of the compounds existing as racemic mixtures or optical isomer dueto the existence of asymetric carbon atoms in the acid moiety and in thealcohol moiety.

In the case when X₁ and X₂ are identical, to determine the stericconfiguration of the asymetric carbon atoms in the 1- and 3-position ofthe cyclopropane ring as well as to determine the structure of thealcohol moiety (which can contain one or more asymetric carbon atomsand/or one or more double bonds), the two diasteroisomeric forms of theesters of formula I or the corresponding free acids due to the existenceof the asymetric carbon atoms in the 1'-position can exist and areeffectively characterized by their RMN Spectrum or by their rate ofmigration in thin-layer chromatography and the two diasteroisomers areindicated as the A and B isomers.

Among the preferred carboxylic acids K of the invention for theformation of the esters of formula I are2,2-dimethyl-3-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-dichloro-2',2'-difluoroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-diiodo-2',2'-difluoroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-diiodo-2',2'-dichloroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-diiodo-2',2'-dibromoethyl)-cyclopropane-1-carboxylicacids, 2,2-dimethyl-3-(1',2',2'-tribromoethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-dichloro-2'-bromoethyl)-cyclopropane-1-carboxylicacids, 2,2-dimethyl-3-(1',2',2'-trichloroethyl)-cyclopropane-1-carboxylic acids,2,2-dimethyl-3-(1',2'-dibromo-2'-chloroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-dichloro-2'-fuoroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-dibromo-2'-fluoroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-diiodo-2'-fluoroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-diiodo-2'-chloroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-diiodo-2'-bromoethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2',2'-trichloro-2'-fluoroethyl)-cyclopropane-1-carboxylicacids,2,2dimethyl-3-(1',2'-dibromo-2'-chloro-2'-fluoroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2',2'-trichloro-2'-bromoethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2',2'-tribromo-2'-chloroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2',2'-tribromo-2'-fluoroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-dichloro-2'-bromo-2'-fluoroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-diiodo-2'-chloro-2'-fluoroethyl)-cyclopropane-1-carboxylicacids,2,2-dimethyl-3-(1',2'-diiodo-2'-bromo-2'-fluoroethyl)-cyclopropane-1-carboxylicacids and2,2-dimethyl-3-(1',2'-diiodo-2'-bromo-2'-chloroethyl)-cyclopropane-1-carboxylicacids.

It is to be understood that the esters of formula I may be prepared fromcyclopropane carboxylic acids of (1S, cis) or (1S, trans) structure aswell as dl cis [equimolar mixture of (1R, cis) and (1S, cis)] or dltrans [equimolar mixture of (1R, trans) and (1S, trans)] or mixtures ofacids of dl-cis and dl-trans structure. The esters of the invention arepreferably formed from cyclopropane carboxylic acids of (1R, cis) or(1R, trans) structure as well as acids of dl-cis or dl-trans structure.

Examples of suitable alcohols used to form the esters of formula I arebenzyl alcohol, 2,5-dimethyl-4-allylbenzyl alcohol,5-benzyl-3-furyl-methanol, 5-(propyn-2'-yl)-2-methyl-3-furyl-methanol(kikuthrol), 5-(propyn-2'-yl)-2-furyl-methanol-(prothrol),1-oxo-2-allyl-3-methyl-cyclopent-2-ene-4-ol (allethrolone),1-oxo-2-(2',4'-pentadienyl)-3-methylcyclopent-2-ene-4-ol,1-oxo-2-(2'-butenyl)-3-methyl-cyclopent-2-ene-4-ol, 3-phenoxy-benzylalcohol, α-cyano-3-phenoxybenzyl alcohol, α-ethynyl-3-phenoxy-benzylalcohol and 3,4,5,6-tetrahydro-phthalimidomethyl alcohol and especiallythe optically active form of the alcohols possessing an asymetric carbonatom.

Among the preferred compounds of formula I are those wherein X₁ and X₂are identical and are selected from the group consisting of fluorine,bromine or chlorine; those wherein X₂ is different from X₁ ; thosewherein R is derived from 5-benzyl-3-furyl-methanol,1-oxo-2-allyl-3-methyl-cyclopent-2-en-4-yl alcohol, 3-phenoxy-benzylalcohol or α-cyano-3-phenoxy-benzyl alcohol with the alcohol beingracemic mixtures or optically active isomers; and those wherein X₁ andX₂ are identical and are selected from the group consisting of bromine,chlorine and fluorine and R is derived from 5-benzyl-3-furyl-methanol,1-oxo-2-allyl-3-methyl-cyclopent-2-en-4-yl alcohol, 3-phenoxy-benzylalcohol or α-cyano-3-phenoxy-benzyl alcohol with the alcohol being inracemic or optically active form.

Particularly preferred compounds of formula I either in the form oftheir A isomer or B isomer due to the existence of a 1'-asymetricalcarbon atom or mixtures of said isomers are (S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylateand (S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylateas well as the other esters produced in the following examples either inthe form of their A or B isomer and mixtures thereof.

The invention is also intended to include the esters of formula I in theform of mixtures of the stereoisomers of cis and trans structure in anyproportions. Among these particularly preferred are mixtures of cis andtrans structure in weight proportions of 20/80, 50/50 and 80/20.

The novel process of the invention for the preparation of the esters offormula I comprises reacting an ester of the formula ##STR5## wherein R,X₁ and X₂ have the above definition which may be in isomer form with achlorination, bromination or iodoration agent capable of adding the saidhalogen across the double bond of the side chain of the cyclopropanecarboxylic acid and this process is indicated as process α.

The halogenation agent is preferably chlorine, bromine or iodine and thereaction is preferably effected in an organic solvent not effected bythe halogenating agent such as, acetic acid, methylene chloride, carbontetrachloride or chloroform.

A process of the invention for the preparation of compounds of formula Icomprises reacting an acid of the formula ##STR6## wherein X₁ and X₂have the above definition which may be in isomer form with achlorination, bromination or iodination agent to form a compound of theformula ##STR7## and reacting the said acid or functional derivativethereof with an alcohol of the formula R--OH or a functional derivativethereof wherein R has the above definition and this process isdesignated as process β.

The halogenation step is effected as in process α and the acid offormula IV is preferably converted to a functional derivative such asthe acid chloride, acid anhydride, mixed acid anhydride, lower alkylester, metal salt or organic base salt thereof and the alcohol may beused in the form of its bromide, chloride or sulfonate.

In a variation of the β process which will be designated as process γ, afunctional derivative of the carboxylic acid of formula III is reactedwith a brominating, chlorinating or iodinating agent to form thecorresponding functional derivative of the acid of formula IV which isthen reacted with the alcohol ROH to form the corresponding ester offormula I.

The halogenation step is effected as in process α and the esterificationis effected as in process β. The functional derivative of the acid offormula III may be the acid chloride, acid anhydride or mixed acidanhydride. When the functional derivative of the acid of formula IV isreacted with the alcohol, the reaction is preferably effected in thepresence of a basic catalyst. When a metal salt of the acid of formulaIV such as an alkali metal, silver or triethylamine salt is used, thealcohol is used in the form of a functional derivative such as itschloride, bromide or sulfonate. Other classical esterification processesmay be used to form the esters of formula I.

In processes β and γ, the functional derivative is preferably the acidchloride of formula IV and the esterification of the alcohol ROH ispreferably effected in the presence of a tertiary base such as pyridineor triethylamine.

In general, the acids of formula III and the esters of formula II andthe functional derivatives of the acids of formula III used as thestarting materials are described in the literature such as French Pat.No. 2,185,612 and No. 2,240,914 or can be prepared by processesanalogous to those described therein. When X₁ and X₂ are differenthalogens, the said esters, acids and their functional derivatives aredescribed in the thesis of Brown (Denton, Texas) of December 1974entitled "Structure-Activity Studies of Halopyrethroids" or by methodsanalogous thereto.

It is understood that the esters of formula II and the acids of formulaIII and their functional derivatives used as starting materials exist innumerous isomeric forms due to the asymetric carbon atoms in thecyclopropane ring and in the case of esters of formula II due to thepossible presence of one or more asymetric carbon atoms and/or one ormore double bonds leading to E-Z isomers in the alcohol moiety.

The novel pesticidal compositions of the invention are comprised of apesticidally effective amount of at least one compound of formula I andan inert carrier. The compositions may also have one or more pesticidalagents and may be in the usual form of powders, granules, suspensions,emulsions, solutions, aerosol solutions, combustible strips or baits orany other classical form. The compositions preferably contains 0.005 to10% by weight of the active material.

The compositions may contain, in general, a vehicle and/or a non-ionicsurface active agent to ensure a uniform dispersion of substances of themixture. The vehicle may be a liquid such as water, alcohol,hydrocarbons or other organic solvents or a mineral, animal or vegetableoil; a powder such as talc, clays, silicates or kieselguhr; or acombustible solid such as tabu powder or pyrethrum residue.

The compositions possess a remarkable insecticidal activity,particularly an extremely intense lethal activity and a very goodstability to atmospheric agents such as heat, light and humidity. Thecompositions are particularly useful against insects in the agriculturalfield and are for example, effective against aphis, larvae ofLepidoptera and Coleoptera.

The compositions when used in agriculture are preferably used at a rateof 1 to 100 g of active material per hectare and due to their rapidaction, the compositions are also useful as insecticides for householduse. Tests have shown the compositions to be useful against housefliesand Spodoptera Littoralis as well as against larvae of EpilachnaVarivestris, against Sitophilus Granarius, Tribolium Castaneum andBlatella Germanica. Preferably, the compounds of formula I are in theform of their A or B isomers due to the existence of the asymetriccarbon atom in the 1'-position or in the form of mixtures of the saidisomers.

To increase the insecticidal activity, the compositions preferablycontain a classic synergist for pyrethrum type compounds such as1-(2,5,8-trioxa-dodecyl-2-propyl-4,5-methylenedioxy)-benzene [piperonylbutoxide], N-(2-ethyl heptyl)-bicyclo[2,2-1]-5-heptene-2,3-dicarboximide orpiperonyl-bis-2-(2'-n-butoxyethoxy)-ethyl acetal [tropital] in a weightratio of 1 to 20 parts of synergist per part of active material. Thepreferred synergist is piperonyl butoxide.

The pesticidal compositions are also useful for combatting nematodes andacarids and tests have shown the compositions to be effective againstTetranychus Urticae and Ditylenchus Myceliophagus.

The compositions for nematocidal and acaricidal use may be in the formof powders, granules, suspensions, emulsions or solutions and maycontain other pesticidal agents. For acaricidal use, the preferredcompositions are wettable powders for foliar spraying containing 1 to80% by weight of the active ingredient or liquids for foliar sprayingcontaining 1 to 500 g/liter of active ingredient or powders for foliarpowdering containing 0.05 to 3% by weight of the active ingredient. Fornematocidal use, the compositions preferably are sols containing 300 to500 g/liter of active ingredient. The usual dosage for both uses is 1 to100 g of active material per hectare.

For acaricidal and nematocidal use, the preferred compounds of formula Iare the A and B isomers of (S)α-cyano -3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylateand the A and B isomers of (S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate.

The anti-acarien activity of the compositions of the invention permittheir use in the form of pharmaceutical compositions for veterinary useto combat parasitic acariens in animals and particularly to combatixodides and parasitic sarcoptides in animals. Tests have shown thecompositions containing at least one compound of formula I to beeffective against Rhipicephalus Sanguineus in dogs.

The compositions of the invention are also useful in animals to combatvarious types of mange such as sarcoptic mange, psoroptic mange andchorioptic mange and are also useful to combat various types of tickssuch as ticks of the Boophilus species, the Hyalomnia species, Amblyomaspecies and the Rhipicephalus species.

The anti-acarienal compositions are useful in veterinary medicine tocombat infections due to acariens and may contain more than one activecompound of formula I. The compositions may be administered externallyas well as orally, rectally or parenterally. The compositions may alsocontain a synergist for pyrethrum type compounds. The compositions mayalso be in the form of an addition to animal feed. For example, theanimal feed may contain 0.002 to 0.4% by weight of (S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate.

The novel antifungal compositions of the invention are comprised of anantifungally effective amount of at least one compound of the formula##STR8## wherein X₁, X₂ and X₃ have the above definition and an inertcarrier. The compositions may contain other pesticidal agent and are inthe form of powders, granules, suspensions, emulsions, solutions,aerosol solutions or other known types of preparations. The compositionspreferably are in the form of sprayable powders containing 25 to 95% byweight of active material or sprayable powders or liquids in a soilcontaining 10 to 30% by weight of the active material.

The compositions may contain besides the active ingredient, a vehicleand/or a non-ionic, surface-active agent to ensure a uniform dispersionof the ingredients of the mixture. The vehicle may be a liquid such aswater, alcohol, hydrocarbons or other organic solvents or a mineral,vegetable or animal oil or a powder such as talc, silicates, clays orkieselguhr.

The antifungal compositions are useful in the agricultural field tocombat pathogenic fungi in the vegetation. Tests have shown thecompositions to be useful against Fusarium Roseum, Botrytis Cinerea,Phoma Specus and Penicillium Roqueforti. The preferred activeingredients are mixtures of the A and B isomers of (S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1'(RS),2,2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylateand mixtures of the A and B isomers of (S)α-cyano -3-phenoxy-benzyl2,2-dimethyl-3S-(1'(RS),2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate.

The invention permits the obtaining of novel acids of formula IV andtheir functional derivatives, especially the acid chlorides in theirvarious isomer forms. The said acids are useful intermediates in theprocess of the invention to obtain the compounds of formula I.

In the following examples there are described several preferredembodiments to illustrate the invention. However, it is to be understoodthat the invention is not intended to be limited to the specificembodiments.

EXAMPLE 1 A and B isomer of (S) α-cyano-3-phenoxy-benzyl 2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate

A solution of 2.4 g of bromine in 15 ml of carbon tetrachloride wasadded to a solution of 7.57 g of (S) α-cyano -3-phenoxy-benzyl2,2-dimethyl-3R-(2',2'-dibromovinyl)-cyclo-propane-1R-carboxylate in 100ml of carbon tetrachloride and the mixture was stirred for 45 minutes at20° C. and was evaported to dryness under reduced pressure. The 10 g ofresidue was chromatographed over silica gel and elution with a 1--1benzene-petroleum ether (b.p.-35°-75° C.) mixture yielded 4.12 g ofisomer A of (S) α-cyano-3-phenoxy-benzyl 2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate followedby 4 g of isomer B of the said ester. Isomers A and B had a specificrotation of [α]_(D) ²⁰ =-53° (c=0.5% in benzene and +111° (c=0.6% inbenzene), respectively.

Characteristics of Isomer A

Analysis: C₂₂ H₁₉ Br₄ NO₃ ; molecular weight=665.037 Calculated: %C39.73; %H 2.88; %Br 48.06; %N 2.11; Found: %C 39.9; %H 2.9; %Br 48.2; %N2.1.

IR Spectra (chloroform):

absorptions at 1740 cm⁻¹ (ester); at 1615, 1588, 1573 and 1488 cm⁻¹(aromatic ring).

RMN Spectrum

peaks at 1.25-1.33 ppm (hydrogen of 2-methyl of cyclopropane at 1.75 to2.17 ppm (hydrogen at 1- and 3-positions of cyclopropane); at 5.19-5.55ppm (hydrogen at 1'-position of lateral chain); at 6.38 ppm (benzylichydrogen); and at 6.91 to 7.59 ppm (hydrogens of aromatic ring).

Circular Dichrosim (dioxane)

Δ.sup.ε =-3 at 224 nm

Δ.sup.ε =-4.5 at 237 nm

Δ.sup.ε =-0.05 at 290 nm

more mobile in thin layer chromatography

Characteristics of Isomer B

Analysis: C₂₂ H₁₉ Br₄ NO₃ ; molecular weight=665.037 Calculated: %C39.73; %H 2.88; %Br 48.06; %N 2.11; Found: %C 39.8; %H 3.0; %Br 48.1; %N2.0

IR Spectrum (chloroform)

absorption at 1743 cm⁻¹ (ester) and at 1615, 1588, 1573 and 1488 cm⁻¹(aromatic ring).

RMN Spectrum

peaks at 1.24-1.40 ppm (hydrogens of 2-methyl of cyclopropane) at 1.83to 2.25 ppm (hydrogens at 1 and 2 of cyclopropane); at 3.98-5.20 ppm(hydrogen in 1'-position of side chain); at 6.39 ppm (benzylichydrogen); and at 6.92 to 7.52 ppm (hydrogens of aromatic ring).

Circular Dichroism (dioxane)

Δ.sup.ε =+4.7 at 223 nm

Δ.sup.ε =+4.2 at 247 nm

less mobile in thin-layer chromatography

EXAMPLE 2 A and B isomers of (S) α-cyano-3-phenoxy-benzyl 2,2-dimethyl-3S-(2',2'-dichloro-1',2'-dibromo-ethyl)-cyclopropane-1R-carboxylate

A solution of 6.55 g of bromine in 20 ml of carbon tetrachloride wasadded over about 10 minutes to a solution of 17.06 g of (S)α-cyano-3-phenoxy-benzyl 2,2-dimethyl-3R-(2',2'-dichlorovinyl)-cyclopropane-1R-carboxylate in 200 ml of carbontetrachloride and the mixture was stirred for 48 hours at 20° C. and wasevaporated to dryness under reduced pressure. The 23.8 g of raw residuewas chromatographed over silica gel and elution with a 7-3benzene-cyclohexane mixture yielded 10.4 g of isomer A (more mobile inthin-layer chromotography) of (S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1R-carboxylateand 10 g of isomer B of the same ester (less mobile in thin layerchromatography). Isomer A and B had a specific rotation of [α]_(D) =-61°(c=0.5% benzene) and +119° (c=1.0% in benzene) respectively.

Characteristics of isomer A

Analysis: C₂₂ H₁₉ Br₂ Cl₂ NO₃ ; molecular weight=576.125 Calculated: %C:45.85; %H: 3.3; %Br: 27.74; %Cl: 12.3; %N: 2.4; Found: %C: 45.8; %H:3.3; %Br: 27.7; %Cl 12.3; %N 2.3.

IR Spectrum (chloroform)

Absorption at 1738⁻¹ (ester) and at 1485, 1585 and 1610⁻¹ (aromaticring)

RMN Spectrum

peaks at 1.29-1.37 ppm (hydrogens of geminal methyls of cyclopropane);at about 2.05 ppm (hydrogens of 1- and 3-positions of cyclopropane); at5.20-5.29-5.37-5.45 ppm (hydrogens fixed on asymetric carbon of sidechain); at 6.45 ppm (benzylic hydrogen); and at 7.0 to 7.6 ppm(hydrogens of aromatic ring)

Circular dichroism (dioxane)

Δ.sup.ε =-8 at 221 nm (inflex.)

Δ.sup.ε =+0.14 at 289 nm (max.)

Characteristics of B isomer

Analysis: C₂₂ H₁₉ Br₂ Cl₂ NO₃ ; molecular weight=576.125 Calculated: %C:45.86; %H: 3.3; %Br: 27.7; %Cl: 12.3; %N: 2.4; Found: %C: 46.2; %H: 3.4;%Br: 27.6; %Cl: 12.2; %N: 2.30.

IR Spectrum

absorption at 1740 cm⁻¹ (ester) and at 1610, 1585 and 1485 cm⁻¹(aromatic ring)

RMN Spectrum

peaks at 1.25-1.38 ppm (hydrogens of geminal methyls of cyclopropane);at 1.87 to 2.3 ppm (hydrogens of 2- and 3-positions of cyclopropane); at4.97-5.01-5.11-5.16 ppm (hydrogen fixed to asymetric carbon of sidechain); at 6.46 ppm (benzyl hydrogen) and at 7 to 7.67 ppm (hydrogens ofaromatic ring).

Circular dichroism (dioxane)

Δ.sup.ε =+9 at 220-221 nm (max.)

Δ.sup.ε =+0.23 at 289 nm (max.)

EXAMPLE 32,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxyliqueacide chloride. STEP A:2,2-dimethyl-3S-(1',2',2',2'-tetrabromomethyl)-cyclopropane-1R-carboxylicacid

A solution of 10.4 g of bromine in 22 ml of carbon tetrachloride wasadded to a mixture of 19.4 g of 2,2-dimethyl-3S-(2',2'-dibromovinyl)-cyclopropane-1R-carboxylic acid in 150 ml ofcarbon tetrachloride and the mixture was stirred at 20° C. for one hourand was evaporated to dryness under reduced pressure. The 31.4 g of rawproduct with a melting point of 145° C. was crystallized from 110 ml ofcarbon tetrachloride to obtain 22.12 g of2,2-dimethyl-3S-(1',2',2',2'-tetrabromo-ethyl)-cyclopropane-1R-carboxylicacid melting at 150° C.

The product was determined by RMN spectrum to be mixture of A and Bisomers which was revealed by one compound (corresponding to about 2/3of the mixture) presenting peaks at 1.31-1.43 ppm corresponding tohydrogens of geminal methyl groups and at 5.33 to 5.66 ppm correspondingto hydrogen fixed on an asymetrical monobrominated carbon and a secondcompound (about 1/3 of the mixture) presenting peaks at 1.28-1.48 ppmcorresponding to hydrogens of geminal methyl groups and at 4.24 to 5.34ppm corresponding to hydogen fixed on an asymetrical monobrominatedcarbon. In the mixture, there were also peaks at 1.67 to 2.17 ppm(hydrogens at 1- and 3-positions of cyclopropane) and towards 11.25 ppm(mobile hydrogen of carboxylic group).

Analysis: C₈ H₁₀ Br₄ O₂ ; molecular weight=457.804 Calculated: %C:20.99; %H: 2.20; %Br: 69.82; Found: %C: 20.9; %H: 2.2; %Br: 70.2.

STEP B:2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclo-propane-1R-carboxylicacid chloride

8.5 ml of thionyl chloride were added to a mixture of 179 ml ofpetroleum ether (b.p. 35°-75° C.) and 0.2 ml of dimethylformamide andafter heating the mixture to reflux, a mixture of 35.76 g of the productof Step A in 150 ml of methylene chloride was added thereto. The mixturewas stirred at reflux for 2 hours and was then cooled and evaporated todryness. The residue was taken up in toluene and the solution wasevaporated to dryness under reduced pressure to obtain 38 g of raw2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylicacid chloride melting at 88° C. which was used as is for the next step.

EXAMPLE 4 (R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2',2',2',-tetrabromoethyl)-cyclopropane-1R-carboxylate

Using the procedure of Example 1, (R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(2',2'-dibromovinyl)-cyclopropane-1R-carboxylate wasreacted with bromine to obtain a mixture of the A and B isomers of (R,S)α-cyano-3-phenoxybenzyl2,2-dimethyl-3R-(1',2',2',2'-tetrabromomethyl)-cyclo-propane-1R-carboxylate.

I.R. Spectrum (chloroform)

Absorptions at 1740,1586 and 1485 cm⁻¹

RMN spectrum

peaks at 1.20-1.26-1.35 ppm (hydrogens of 2-methyl of cyclopropane); at4.3-4.48-4.67 ppm (hydrogen in the 1'-position of the side chain oncyclopropane); at 6.48 ppm (hydrogen fixed to same carbon as C=N); andat 6.97 to 7.17 ppm (hydrogens of aromatic ring).

EXAMPLE 5 (R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1R-carboxylate

Using the procedure of Example 1, (R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(2',2'-dichlorovinyl)-cyclopropane-1R-carboxylate andbromine were reacted to form a mixture of the A and B isomers of (R,S)α-cyano-3-phenoxybenzyl2,2-dimethyl-3R-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1R-carboxylate.

I.R. Spectrum (chloroform)

Absorption at 1743, 1588 and 1487 cm⁻¹

RMN Spectrum

peaks at 1.20-1.26-1.32-1.35 ppm (hydrogens of 2-methyl ofcyclopropane); at 1.68-1.77 ppm (hydrogen in 1-position ofcyclopropane); at 1.95-2.42 ppm (hydrogen of 3-position ofcyclopropane); at 4.23-4.25-4.40-4.42-4.57 ppm (hydrogens in 1'-positionof 3-ethyl chain of cyclopropane); at 6.48 ppm (hydrogen fixed to samecarbon as --CN); and at 7.0 to 7.67 ppm (hydrogen of aromatic ring).

EXAMPLE 6 (S) 1-oxo-2-allyl-3-methyl-cyclopent-2-en-4-yl2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylateSTEP A:2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclo-propane-1R-carboxylicacid

Using the procedure of Step A of Example 3,2,2-dimethyl-3S-(2',2'-dibromovinyl)-cyclopropane-1R-carboxylic acid wasbrominated to form a mixture of the A and B isomers of2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylicacid.

RMN Spectrum

peaks at 1.30 to 1.40 ppm (hydrogens of 2-methyls on cyclopropane); at1.65-1.74 and 1.97 to 2.37 ppm (hydrogens at 1-and 3-positions ofcyclopropane); at 4.30-4.47 and 4.47-4.65 ppm (hydrogen in 1'-positionof ethyl); and at 9.63 ppm (carboxyl hydrogen).

STEP B:2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylicacid chloride

Using the procedure of Step B of Example 3, the product of Step A wasreacted with thionyl chloride to obtain 2,2-dimethyl-B3R-(1',2',2',2-tetrabromoethyl)-cyclopropane-1R-carboxylic acid chloridewhich was used as is for the next step.

I.R. Spectrum (chloroform)

Absorption at --1778 cm⁻¹

STEP C: (S) 1-oxo-2-allyl-3-methyl-cyclopent-2-en-4-yl2,2-dimethyl-3R-1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate

(S)1-oxo-2-allyl-3-methoxy-cyclopent-2-en-4-ol in benzene was stirredunder an inert atmosphere at 20° C. for 15 hours with the product ofStep B in the presence of pyridine. Water was added thereto and theorganic phase was decanted. The aqueous phase was extracted with benzeneand the combined benzene phase were washed with water, sodiumbicarbonate solution and then water 1 N hydrochloric acid and finallywith water. The benzene phase was dried and evaporated to dryness underreduced pressure. The residue was chromatographed over sila gel and waseluted to obtain a mixture of the A and B isomers of (S)1-oxo-2-allyl-3-methylcyclopent-2-en-4-yl2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate.

I.R. Spectrum (chloroform)

Absorptions at 1725, 1710, 1655, 1638, 995 and 918 cm⁻¹

RMN Spectrum

peaks at 1.30-1.32-1.36 ppm (hydrogens of 2-methyls of cyclopropane); at1.98-2.05 (hydrogens at 3-methyl on cyclopropane at 4.83-5.25 ppmhydrogens of terminal methylene of allylic chain of allethrolone); at4.30-4.48 and 4.43-4.67 ppm (hydrogens of lateral 3-ethyl oncyclopropane); and at 5.33-6.17 ppm (hydrogens on 2'-position of allylof allethrolone).

EXAMPLE 7 A and B isomers of 5-benzyl-3-furyl-methyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate

Using the procedure of Step C of Example 6, the acid chloride of Step Bof Example 3 was reacted with 5-benzyl-3-furyl-methanol in the presenceof pyridine to obtain isomers A and B of 5-benzyl-3-furyl-methyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylatewith a specific rotation of [α]_(D) =-104° and +84° (c=0.5% in benzene),respectively. The A isomer was the more mobile in thin layerchromatography.

Characteristics of A isomer RMN Spectrum

peaks at 1.23-1.37 ppm (hydrogens of 2-methyls of cyclopropane) at1.65-2.03 ppm (hydrogens in 1- and 3-positions of cyclopropane); at 3.92ppm (hydrogens of methylene of benzyl); at 4.92 ppm (hydrogens ofmethylene of --COO--CH₂ --);

at 5.27-5.67 ppm (hydrogen in 1'-position of 3-ethyl of cyclopropane);at 5.96 ppm (4-hydrogen of furyl); at 7.25 ppm hydrogens of phenyl) andat 7.33 ppm (2-hydrogen of furyl).

Circular dichroism (dioxane)

Δ.sup.ε =-6.5 at 217 nm

Characteristics of B isomer RMN Spectrum

peaks at 1.20-1.42 ppm (hydrogens of 2-methyls of cyclopropane), at 1.67to 2.17 ppm (hydrogens in 1- and 3-positions of cyclopropane); at 3.92ppm (hydrogens of methyl of benzyl); at 4.95 ppm (hydrogens of methyleneof COOCH₂); at 4.95 to 5.18 ppm (hydrogens in 1'-position of 3-ethyl ofcyclopropane); at 7.25 ppm (hydrogens of aromatic ring of benzyl); andat 7.33 ppm (2-hydrogen of furyl).

Circular dichroism (dioxane)

Δ.sup.ε =+4.30 at 247 nm

EXAMPLE 8 A and B isomers of (S) allethrolone2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate

Using the procedure of Step C of Example 6, the acid chloride of Step Bof Example 3 was reacted with (S) allethrolone in the presence ofpyridine to obtain the A and B isomers of (S) allethrolone2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylatewith a specific rotation of [α]_(D) =-56° and +81° (c=0.6% in benzene),respectively. The A isomer was the more mobile in thin-layerchromatography.

Characteristics of A isomer RMN Spectrum

peaks at 1.28-1.39 ppm (hydrogens of 2-methyls of cyclopropane); at 1.96ppm (hydrogens of 3-methyl of allethrolone); at 4.83-5.16 ppm (hydrogensof terminal methylene of allylic chain); and at 5.33 to 6.16 ppm(hydrogen in 1'-position of 3-ethyl of cyclopropane and 2'-hydrogen ofallyl):

Circular dichroism (dioxane)

Δ.sup.ε =1.84 at 332 nm

Δ.sup.ε =2.06 at 320 nm

Δ.sup.ε =-19 at 225 nm

Characteristics of B isomer

melting point of 110° C.

RMN spectrum

peaks at 1.27-1.47 ppm (hydrogens of 2-methyls of cyclopropane); at 2.07ppm (hydrogens of 3-methyl of allethrolone); at 4.83 to 5.33 ppm(hydrogen at 1'-position of lateral chain in 3-position of cyclopropaneand hydrogens of 2'-methylene of allyl); at 5.5-6.16 ppm (hydrogens in2'-position of allyl); and at 5.15 ppm (hydrogens of 4-position ofallethrolone).

Circular dichroism (dioxane)

Δ.sup.ε =+2.46 at 332 nm

Δ.sup.ε =+2.76 at 320 nm

Δ.sup.ε =+3.79 at 250 nm

Δ.sup.ε =-1.7 at 225 nm

EXAMPLE 9 A and B isomers of 3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate

Using the procedure of Step C of Example 6, the acid chloride of Step Bof Example 3 was reacted with 3-phenoxy benzyl alcohol in the presenceof pyridine to form the mixture of the A and B isomers of3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylatewith a specific rotation of [α]_(D) =-106° (c=0.5% in benzene) and+61.5° (c=2.3% in benzene), respectively. A isomer was the more mobilein thin-layer chromatography and melted at 90° C.

Characteristics of A isomer RMN spectrum

peaks at 0.92-1.37 ppm (hydrogens of 2-methyls of cyclopropane); at1.67-2.08 ppm (hydrogens of 1- and 3-position of cyclopropane); at 5.08ppm (hydrogens of methylene of --COOCH₂); at 5.38-5.56 ppm (1'-hydrogenof 3-ethyl of cyclopropane); and at 6.67 to 7.58 l ppm (hydrogens ofaromatic ring).

Circular dichroism (dioxane)

Δ.sup.ε =-10 at 218 nm

Characteristics of B isomer RMN Spectrum

peaks at 1.22-1.42 ppm (hydrogen of 2-methyls of cyclopropane); at 1.67to 2.08 ppm (1- and 3-hydrogens of cyclopropane); at 4.93 to 5.33 ppm(1'-hydrogen of 3-ethyl of cyclopropane); at 5.15 ppm (hydrogens ofmethylene of COOCH₂); and at 6.75 to 7.58 ppm (hydrogens of aromaticring).

Circular dichorism (dioxane)

Δ.sup.ε =+4.6 at 247 nm

EXAMPLE 10 (S) allethrolone2,2-dimethyl-3R-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1R-carboxylateSTEP A:2,2-dimethyl-3R-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1R-carboxylicacid

Using the procedure of Step A of Example 3,2,2-dimethyl-3S-(2',2'-dichlorovinyl)-cyclopropane-1R-carboxylic acidwas brominated to obtain a mixture of A and B isomers of2,2-dimethyl-3R-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1R-carboxylicacid.

RMN Spectrum

peaks at 1.17-1.37 ppm (hydrogens of 2-methyls of cyclopropane); from1.65-1.73 ppm to 1.93-2.03 ppm (hydrogens in the 1-position ofcyclopropane); and at 4.23-4.45 and at 4.45-4.62 ppm (1'-hydrogen of3-ethyl of cyclopropane).

STEP B:2,2-dimethyl-3R-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1R-carboxylicacid chloride

Using the procedure of Step B of Example 3, the product of Step A wasreacted with thionyl chloride to obtain2,2-dimethyl-3R-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1R-carboxylicacid chloride.

I.R. Spectrum (chloroform)

Absorption at 1777 cm⁻¹

STEP C: (S) allethrolone2,2-dimethyl-3R-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1R-carboxylate

Using the procedure of Step C of Example 6, the product of Step B wasreacted with (S) allethrolone in the presence of pyridine to obtain amixture of the A and B isomers of (S) allethrolone2,2-dimethyl-3R-(2',2'-dichloro1',2'-dibromoethyl)-cyclopropane-1R-carboxylate.

RMN Spectrum

peaks at 1.30-1.34 ppm (hydrogens of 2-methyls of cyclopropane); at1.63-3.0 ppm (hydrogens in 1- and 3-position of cyclopropane); at 2.05ppm (hydrogens of 3-methyl of allethrolone); at 1.95-3.03 ppm (hydrogensof 1'-methylene of allyl chain); at 4.25-4.43-4.61 ppm (1'-hydrogen of3-ethyl of cyclopropane); at 4.25 ppm (hydrogens of terminal methyleneof allyl chain); at 4.83-5.41 ppm (2'-hydrogen of allyl chain); and at5.83 ppm (hydrogens in 4-position of allethrolone).

EXAMPLE 11 (RS)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(2',2'-dibromo-1',2'-dichloroethyl)-cyclopropane-1R-carboxylateSTEP A:2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylicacid

11.8 g of chlorine were bubbled into 30 ml of carbon tetrachloride at-15° C. and then a solution of 24 g of2,2-dimethyl-3R-(2',2'-dibromovinyl)-cyclopropane-1R-carboxylic acid in37 ml of carbon tetrachloride was slowly added thereto at -10° C. Themixture was stirred for 90 minutes at 0° C. and 2 hours at 25° C. andwas then evaporated to dryness under reduced pressure. The residue wascrystallized from carbon tetrachloride to obtain 7.4 g of the A and Bisomers of2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylicacid melting point of 134° C.

RMN Spectrum

peaks at 1.32-1.44 ppm and at 1.28-1.48 ppm (hydrogens of 2-methyls ofcyclopropane); at 5.08-5.45 and 4.67-5.0 ppm (1'-hydrogen of 3-ethyl ofcyclopropane); and at 10.1 ppm (carboxyl hydrogen).

STEP B:2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylicacid chloride

Using the procedure of Step B of Example 3, the product of Step A wasreacted with thionyl chloride in the presence of pyridine to obtain2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylicacid chloride which was used as is for the next step.

STEP C: α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate

Using the procedure of Step C of Example 6, the product of Step B wasreacted with α-cyano-3-phenoxy-benzyl alcohol in the presence ofpyridine to obtain a mixture of the A and B isomers ofα-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate.

RMN Spectrum

peaks at 1.23-1.52 ppm (hydrogens of 2-methyls of cyclopropane); at 1.77to 2.11 ppm (1-and 3-hydrogens of cyclopropane); at 4.72-4.88 and5.02-5.21 ppm (1'-hydrogen of 3-ethyl of cyclopropane); at 6.40 to 6.43ppm (hydrogen attached to same carbon as --CN); and at 6.94 to 7.66 ppm(hydrogens of aromatic ring).

EXAMPLE 12 (S) allethrolone2,2-dimethyl-3S-(2',2'-dibromo-1',2'-dichloroethyl)-cyclopropane-1R-carboxylate

Using the procedure of Step C of Example 6, the acid chloride of Step Bof Example 11 was reacted with (S) allethrolone to obtain a mixture ofthe A and B isomers of (S) allethrolone2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate.

RMN Spectrum

peaks at 1.25-1.45 and 1.29-1.40 ppm (hydrogens of 2-methyl ofcyclopropane); at 1.96 ppm (hydrogens of 3-methyl of allethrolone); at2.96-3.03 ppm (hydrogens of 1'-methylene of allyl chain); at 4.83-5.16ppm (hydrogens of terminal methylene of allyl chain); at 5.25-5.36 ppm(1'-hydrogen of 3-ethyl of cyclopropane); and at 5.5 to 6.0 ppm(4-hydrogens of allethrolone and 2'-hydrogen of allyl chain).

EXAMPLE 13 (R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate

Using the process of Step C of Example 6, the acid chloride of Step B ofExample 10 was reacted with (R,S)α-cyano-3-phenoxy-benzyl alcohol toobtain a mixture of the A and B isomers of (R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate

RMN Spectrum:

peaks at 1.22-1.27-1.37-1.4-1.45 ppm (hydrogens of 2-methyls ofcyclopropane); at 1.67-2.5 ppm (1- and 3-hydrogen of cyclopropane); at3.67-4.5 ppm (1'-hydrogen of 3-ethyl of cyclopropane); at 6.52 ppm(hydrogen attached to same carbon as --CN); and at 7.0-7.67 ppm(hydrogens of aromatic ring).

EXAMPLE 14 (S) allethrolone2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylateSTEP A:2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl-cyclopropane-1R-carboxylicacid

Using the procedure of Step A of Example 3,2,2-dimethyl-3R-(2',2'-difluorovinyl)-cyclopropane-1R-carboxylic acidwas reacted with bromine at -60° C. to obtain a mixture of the A and Bisomers of2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylicacid melting at 122° C.

RMN Spectrum:

peaks at 1.33-1.36 ppm (hydrogens of 2-methyls of cyclopropane); at1.60-2.23 ppm (1- and 3-hydrogens of cyclopropane); at 3.75-4.37 ppm(1'-hydrogen of 3-ethyl of cyclopropane); and at 10.96 ppm (carboxylhydrogen).

STEP B:2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)cyclopropane-1-carboxylicacid chloride

Using the procedure of Step B of Example 3, the product of Step A wasreacted with thionyl chloride to form2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylicacid chloride which was used as is for the next step.

STEP C: (S) allethrolone2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylate

Using the procedure of Step C of Example 6, the acid chloride of Step Bwas reacted with (S) allethrolone in the presence of pyridine to obtaina mixture of the A and B isomers of (S) allethrolone2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylate.

RMN Spectrum

peaks at 1.32 ppm (hydrogens of 2-methyls of cyclopropane); at 3.26-1.68and 1.73 to 2.19 ppm (1-hydrogens of cyclopropane); at 1.20 ppm(hydrogens of 3-methyl of allethrolone); at 2.93-3.05 ppm (hydrogens of1'-methylene of allyl chain); at 4.83-5.25 ppm (hydrogens of terminalmethylene of allyl chain); at 3.58-4.33 ppm (1'-hydrogen of 3-ethyl ofcyclopropane); peaks at 4.83-5.25 ppm (2'-hydrogen of allyl chain); andat 5.83 ppm (4-hydrogens of allethrolone).

EXAMPLE 15 (R,S)α(-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylateSTEP A:2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylicacid

Using the procedure of Step A of Example 3,2,2-dimethyl-3R-(2',2'-dichlorovinyl)-cyclopropane-1R-carboxylic acidwas reacted with bromine to obtain a mixture of the A and B isomers of2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylicacid.

RMN Spectrum

peaks at 1.26-1.30 and at 1.41-1.42 ppm (hydrogens of 3-methyls ofcyclopropane); at 1.83-2.17 ppm (1- and 3-hydrogens of cyclopropane); at4.83-5.58 ppm (1'-hydrogen of 3-ethyl of cyclopropane); and at 8.17 ppm(carboxyl hydrogen).

STEP B:2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylicacid chloride

Using the procedure of Step B of example 3, the product of Step A wasreacted with thionyl chloride to obtain2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1-R-carboxylicacid chloride which was used as is for the next step.

STEP C: (R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate

Using the procedure of Step C of Example 6, the product of Step B wasreacted with (RS)α-cyano-3-phenoxy-benzyl alcohol to obtain a mixture ofthe A and B isomers of (R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylte

EXAMPLE 16 (R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylateSTEP A:2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylateacid

A solution of 0.9 ml of bromine in 10 ml of carbon tetrachloride wasadded over 30 minutes to a mixture of 5 g of2,2-dimethyl-3R-(2',2'-dibromovinyl)-cyclopropane-1R-carboxylic acid in30 ml of carbon tetrachloride and the mixture was stirred for 90 minutesand was evaporated to dryness under reduced pressure to obtain 8.9 g ofraw2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylicacid.

STEP B:2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylicacid chloride

8.9 g of2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylicacid were added to a mixture of 40 ml of petroleum ether (b.p. =35°-70°C.) and 10 ml of thionyl chloride and the mixture was refluxed for 3hours and the mixture was evaporated to dryness to obtain the raw2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylicacid chloride which was used as is for the next step.

STEP C: (R,5)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate

A solution of the product of Step B in 40 ml of benzene was added over15 minutes at 0° C. to a mixture of 7 g of (RS) α-cyano-3-phenoxy-benzylalcohol in 5 ml of benzene and 10 ml of pyridine and the mixture wasstirred at 20° C. for 16 hours and was then acidified to a pH of 1 withaqueous dilute hydrochloric acid. The mixture was extracted with benzeneand the organic phase was washed with water, dried over magnesiumsulfate and evaporated to dryness. The residue was chromatographed oversilica gel and was eluted with benzene to obtain 7.33 g of (RS)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate.

Analysis: C₂₂ H₁₉ O₅ NBr₄ ; molecular weight=665.05 Calculated: %C:39.73; %H: 2.88; %N: 2.10; %Br 48.06; Found: %C: 39.7; %H: 3; %N: 2.2;%Br 47.4.

I.R. Spectrum (chloroform)

Absorption at 1743 cm⁻¹ (>C═0); at 1613, 1588 and 1477 cm⁻¹ (aromaticring).

U.V. Spectrum (ethanol):

Inflex. towards 230 nm E₁ ¹ =194

Inflex. towards 270 nm E₁ ¹ =36

Max. at 278 nm E₁ ¹ =37

Inflex. towards 285 nm E₁ ¹ =28

RMN Spectrum (deuterochloroform)

peaks at 1.23-1.5 ppm (hydrogens of geminal methyls); at 1.83-2.16 ppm(hydrogens of cyclopropane); at 4.82-5.5 ppm (1'-hydrogen of 3-ethyl ofcyclopropane); at 6.37-6.42 ppm (hydrogen attached to same carbon as-CN); and at 6.83-7.58 ppm (hydrogens of aromatic ring).

EXAMPLE 17 3-phenoxy-benzyl2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylateSTEP A:2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylicacid

Using the procedure of Step A of Example 16,2,2-dimethyl-3S-(2',2'-dibromovinyl)-cyclopropane-1R-carboxylic acid wasreacted with bromine to obtain a mixture of A and B isomers of2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)cyclopropane-1R-carboxylicacid.

RMN Spectrum (deuterochloroform)

peaks at 1.30-1.40 ppm (hydrogens of 2-methyls of cyclopropane); at1.65-1.74 and 1.97-2.37 ppm (1- and 3-hydrogens of cyclopropane); at4.30-4.47 and at 4.47-4.65 ppm of (1'-hydrogen of 3-ethyl ofcyclopropane); and at 9.63 ppm (carboxyl hydrogen).

STEP B:2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylicacid chloride

Using the procedure of Step B of Example 16, the product of Step A wasreacted with thionyl chloride to obtain2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylicacid chloride which was used as is for the next step.

STEP C: 3-phenoxy-benzyl2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate

2.4 g of 3-phenoxy-benzyl alcohol were added at 0° C. to a solution of 5g of the product of Step B in 20 ml of benzene and then 4 ml of pyridinewere progressively added thereto. The mixture was stirred at 20° C. for48 hours and was then poured into an aqueous hydrochloric acid solution.The mixture was extracted with benzene and the benzene extract waswashed with aqueous sodium bicarbonate solution, with water, dried oversodium sulfate and concentrated to dryness under reduced pressure toobtain 6.2 g of residue which was chromatographed over silica gel.Elution with 9-1 petroleum ether (b.p.=35°-75° C.)-ethyl ether mixtureyielded 3.68 g of a mixture of the A and B isomers of 3-phenoxy-benzyl2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)cyclopropane-1R-carboxylate.

Analysis: C₂₁ H₂₀ Br₄ O₃ ; molecular weight=640.03 Calculated: %C:39.41; %H: 3.15; %Br 49.94; Found: %C: 39.9; %H: 3.2; %Br 50.2.

I.R. Spectrum (chloroform)

Absorption at 1728 cm⁻¹ (carbonyl) and at 1615, 1590 and 1490 cm⁻¹(aromatic ring).

RMN Spectrum (deuterochloroform)

peaks at 1.26-1.29-1.35 ppm (hydrogens of geminal methyls); at 2.00-2.33ppm (1-hydrogen of cyclopropyl); at 1.70-1.79 ppm (3-hydrogen ofcyclopropyl); at 4.31-4.48-4.50-4.67 ppm (1'-hydrogen of 3-ethyl ofcyclopropane); at 5.17-5.20 ppm (hydrogens of methylene of benzyl); andat 6.92-7.58 ppm (hydrogens of aromatic ring).

EXAMPLE 18 3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylateSTEP A:2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylicacid

11.8 g of chlorine were dissolved in 30 ml of carbon tetrachloride andthen a solution of 16.7 g of2,2-dimethyl-3R-(2',2'-dichlorovinyl)-cyclopropane-1R-carboxylic acid in40 ml of methylene chloride was added thereto at 0° C. The mixture wasstirred at 0° C. for 24 hours and then at 25° C. for 3 hours and theexcess chlorine was removed by bubbling nitrogen through the mixture.The mixture was evaporated to dryness under reduced pressure and theresidue was chromatographed over silica gel. Elution with an 8-2cyclohexaneethyl acetate mixture yielded a product which wascrystallized from petroleum ether (b.p.=35°-75° C.) to obtain 3.14 g of2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylicacid melting at 144° C.

Analysis: CgH₁₀ Cl₄ O₂ ; molecular weight=279.98 Calculated: %C: 34.3;%H: 3.6; %Cl: 50.6; Found: %C: 34.4; %H: 3.7; %Cl: 50.3.

RMN Spectrum (deuterochloroform)

peaks at 1.26-1.42 ppm and 1.30-1.42 ppm (hydrogens of geminal methyls);at 4.67-5.17 ppm and 5.08-5.43 ppm (1'hydrogen of 3-ethyl ofcyclopropane); at 1.67-2.00 ppm of (1- and 3-hydrogens of cyclopropane);and at 10.2 ppm (carboxyl hydrogen).

STEP B:2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)cyclopropane-1R-carboxylicacid chloride

A mixture of 6.75 g of the product of Step A in 60 ml of petroleum ether(b.p.=35°-70° C.) and 8.7 ml of thionyl chloride was refluxed for 41/2hours and was then evaporated to dryness under reduced pressure. Theresidue was added to benzene and the solution was evaporated to drynessto obtain raw2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylicacid chloride which was used as for the next step.

STEP C: 3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylate

A solution of 5.2 g of 3-phenoxy-benzyl alcohol in 50 ml of benzene wasadded at 75° C. to a solution of the product of Step A in 60 ml ofbenzene followed by the addition of 2.6 ml of pyridine and stirring for16 hours at 20° C. The reaction mixture was poured into awater-hydrochloric acid mixture and the mixture was extracted with ethylether. The ether extracts were evaporated to dryness to obtain 11 g ofresidue which was chromatographed over silica gel. Elution with a 1-1benzene-cyclohexane mixture and crystallization from ether gave a firstfraction of 4.6 g of 3-phenoxybenzyl2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylatewith a melting point of 86° C. and a specific rotation of [α]_(D) ²⁰=-86.5° (c=0.5% in benzene).

Analysis: C₂₁ H₂₀ Cl₄ O₃ ; molecular weight=462.20 Calculated: %C:54.56; %H: 4.35; %Cl 30.68; Found: %C: 54.9; %H: 4.5; %Cl: 30.3.

U.V. Spectrum (ethanol)

Inflex. towards 226 nm E₁ ¹ =228

Inflex. towards 266 nm E₁ ¹ =36

Max. at 271 nm E₁ ¹ =41

Max. at 277 nm E₁ ¹ =40

RMN Spectrum (deuterochloroform)

peaks at 1.27-1.4 ppm (hydrogens of geminal methyls of isomer A); at5.13 ppm (hydrogens of ##STR9## of isomer A); at 5.27-5.43 ppm(1'-hydrogen of 3-ethyl of isomer A); at 1.23-1.40 ppm (hydrogens ofgeminal methyls of isomer B); at 5.18 ppm (hydrogens of ##STR10## ofisomer B); at 4.83-5.17 ppm (1'hydrogen of 3-ethyl of isomer B); at1.61-2.03 ppm (1- and 3-hydrogens of cyclopropane); and at 6.92-7.58 ppm(hydrogens of aromatic ring). The said spectrum showed that the productwas about 90% of isomer A and about 10% of isomer B.

Chromatography of the product and crystallization from ether yielded asecond fraction of 3.3 g of 3-phenoxybenzyl2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylatewith a melting point of 62° C. and a specific rotation [α]_(D) ²⁰ =-9°(c=1% in benzene) and the RMN spectrum showed the product to be about60% isomer B and about 40% of isomer A.

I.R. Spectrum (chloroform)

Absorption at 1725 cm⁻¹ (carbonyl) and at 1615, 1590 and 1490 cm⁻¹(aromatic ring).

RMN Spectrum (deuterochloroform)

peaks at 1.23-1.41 ppm (hydrogens of geminal methyls of isomer B); at4.83-5.17 ppm (1'-hydrogen of 3-ethyl of isomer B); at 5.2 ppm(hydrogens of ##STR11## of isomer B); at 1.28-1.4 ppm (hydrogens ofgeminal methyls of isomer A); at 5.27-5.43 ppm (1'-hydrogen of 3-ethylof isomer A); at 5.13 ppm (hydrogens of ##STR12## of isomer A); at1.58-2.08 ppm (1- and 3-hydrogens of cyclopropane); and at 6.9-7.16 ppm(hydrogens of aromatic ring).

EXAMPLE 19 (R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylate

A solution of 4.6 g of R,S, α-cyano-3-phenoxy-benzyl alcohol in 30 ml ofbenzene was added at 5° C. to a solution of2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylicacid chloride [prepared from 5.4 g of the corresponding acid as in StepB of Example 18] in 50 ml of benzene and after adding 2.2 ml ofpyridine, thereto, the mixture was stirred for 48 hours at roomtemperature and was poured into aqueous hydrochloric acid solution. Themixture was extracted with ether and the extracts were evaporated todryness. The residue was chromatographed over silica gel and was elutedwith a 1-2 benzene-cyclohexane mixture to obtain 4.7 g of (R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylatewith a specific rotation of [α]_(d) ²⁰ =-56.5° (c=0.4% in benzene).

Analysis: C₂₂ H₁₉ Cl₄ NO₃ ; molecular weight=487.22 Calculated: %C:54.23; %H: 3.93; %N: 2.87; %Cl: 29.11; Found: %C: 54.3; %H: 3.8; %N:2.8; %Cl: 29.0.

U.V. Spectrum (ethanol)

Inflex. towards 227 nm E₁ ¹ =225

Infex. towards 268 nm E₁ ¹ =35

Infex. towards 272 nm E₁ ¹ =38

Max. at 278 nm E₁ ¹ =43

Inflex. towards 284 nm E₁ ¹ =33

RMN Spectrum (deuterochloroform)

peaks at 1.22-1.43 ppm (hydrogens of geminal methyls); at 1.67-2.08 ppm(1- and 3-hydrogens of cyclopropane); at 4.83-6.47 ppm (1'-hydrogen of3-ethyl of cyclopropane); at 6.38-6.46 ppm (hydrogen or same carbon as--CN); and at 6.92-7.58 ppm (hydrogens of aromatic ring).

EXAMPLE 20 (R,S) allethrolone2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylate

A solution of 4 g of (R,S) allethrolone in 15 ml of benzene was added at5° C. to a solution of2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylicacid chloride (produced from 7 g of the corresponding acid by Step B ofExample 18) in 20 ml of benzene and after the addition of 2.55 ml ofpyridine thereto, the mixture was stirred for 18 hours at 20° C. and waspoured into aqueous hydrochloric acid. The mixture was extracted withether and the ether extracts were evaporated to dryness. The residue waschromatographed over silica gel and was eluted with a 9-1cyclohexane-ethyl acetate mixture to obtain 8 g of (R,S) allethrolone2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)cyclopropane-1R-carboxylatewith a specific rotation of [α]_(d) ²⁰ =-54.7° (c=0.5% in benzene).

Analysis: C₁₇ H₂₀ Cl₄ O₃ ; molecular weight=414.15 Calculated %C: 49.30;%H: 4.87; %Cl: 34.24; Found: %C: 49.5; %H: 4.9; %Cl: 34.1.

U.V. Spectrum (ethanol) Max. at 227 nm E₁ ¹ =334 RMN Spectrum(deuterochloroform)

peaks at 1.31-1.42 ppm (hydrogens of geminal methyls); at 1.62-2.17 ppm(1- and 3-hydrogens of cyclopropane); and at 4.83-6.17 ppm (1-hydrogenof 3-ethyl of cyclopropane).

EXAMPLE 21 (R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylateSTEP A:2,2-dimethyl-3R-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylicacid

A solution of 18.8 g of2,2-dimethyl-3S-(2',2'-dichlorovinyl)-cyclopropane-1R-carboxylic acid in30 ml of methylene chloride was added over 15 minutes at -10° C. to asolution of 13.25 g of chlorine in 30 ml of carbon tetrachloride and theresulting mixture was passed over a refrigerant in which circulated aliquid at -60° C. to condense the nonreacted chlorine. The mixture wasstirred at -10° C. for 90 minutes and then for 90 minutes at 0° C. andexcess chlorine was removed at 20° C. by bubbling nitrogen therethrough.The mixture was evaporated to dryness under reduced pressure and theresidue was chromatographed over silica gel. Elution with a 7-3cyclohexane-ethyl acetate mixture yielded 23 g of2,2-dimethyl-3R-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylicacid which was used as is for the next step.

STEP B: 2,2-dimethyl-3R-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylic acid chloride

12.276 g of the product of Step A were added to a mixture of 30 ml ofpetroleum ether (b.p.=35°-75° C.) and 16 ml of thionyl chloride and themixture was refluxed for 41/2 hours and was then evaporated to drynessunder reduced pressure. The residue was taken up in benzene and thesolution was evaporated to dryness to obtain2,2-dimethyl-3R-(1',2',2',2'tetrachloroethyl)-cyclopropane-1R-carboxylicacid chloride which was used as is for the next step.

STEP C: (R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3B-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylate

A solution of 10.5 g of (R,S) α-cyano-3-phenoxybenzyl alcohol in 20 mlof benzene was rapidly added at 5° C. to a mixture of the product ofStep B in 25 ml of benzene and 4.5 ml of pyridine were rapidly addedthereto. The mixture was stirred at 20° C. for 16 hours and was pouredinto a mixture of ice-water-hydrochloric acid. The mixture was extractedwith ethyl ether and the organic phase was washed with water, dried andevaporated to dryness under reduced pressure. The residue waschromatographed over silica gel and was eluted with a 9-1cyclohexane-ethyl acetate mixture to obtain 14.18 g of (R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylatewith a specific rotation of [α]_(D) ²⁰ =-22.5° (c=0.5% in benzene).

Analysis: C₂₂ H₁₉ Cl₄ NO₃ ; molecular weight=487.21 Calculated: %C:54.2; %H 3.9; %Cl: 29.1; %N 2.9 Found: %C: 54.0; %H: 4.0; %Cl: 29.0; %N:2.7.

I.R. Spectrum (chloroform)

Absorptions at 1742 cm⁻¹ (carbonyl) and at 1610, 1584 and 1484 cm⁻¹(aromatic ring).

U.V. Spectrum (ethanol)

Infex. at 230 nm E₁ ¹ =230

Infex. at 267 nm E₁ ¹ =41

Infex. at 271 nm E₁ ¹ =44

Max. at 277 nm E₁ ¹ =49

Infex. at 283 nm E₁ ¹ =37

Infex. at 305 nm E₁ ¹ =4

RMN Spectrum (deuterochloroform):

peaks at 1.22-1.42 ppm (hydrogens of methyl); at 1.50-2.50 ppm (1- and3-hydrogens at cyclopropane); at 3.66-4.41 ppm (1'-hydrogen at 3-ethylof cyclopropane); at 6.5 ppm (hydrogen on same carbon as --CN); and at7.00-7.66 ppm (hydrogens of aromatic ring).

EXAMPLE 22 3-phenoxy-benzyl2,2-dimethyl-3R-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylate

A solution of 4 g of 3-phenoxy-benzyl alcohol in 15 ml of benzene wasadded at 0° C. to 18.6 ml of a solution of the the acid chloride in 30ml of benzene prepared from 10.4 g of2,2-dimethyl-3R-(1',2',2',2'-tetrachloroethyl)cyclopropane-1R-carboxylicacid and after the addition of 2 ml of pyridine thereto, the mixture wasstirred at 20° C. for 18 hours and was poured into a mixture of ice,water and hydrochloric acid. The mixture was extracted with ethyl etherand the extracts were washed with water, dried over magnesium sulfate,filtered and evaporated to dryness under reduced pressure. The 8.6 g ofresidue was chromatographed over silica gel and was eluted with a 95-5cyclohexane-ethyl acetate mixture and then a 1-1 cyclohexane-benzenemixture to obtain 3-phenoxy-benzyl2,2-dimethyl-3R-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylate.

Analysis: C₂₁ H₂₀ Cl₄ O₃ ; molecular weight=462.20

Calculated: %C: 54.6; %H: 4.4; %Cl: 30.7; Found: %C: 55.2; %H: 4.5; %Cl:29.4.

I.R. Spectrum (chloroform)

Absorption at 1728 cm⁻¹ (carbonyl) and at 1615 and 1587 cm⁻¹ (aromaticring).

U.V. Spectrum (ethanol)

Inflex. at 227 nm E₁ ¹ =245

Inflex. at 266 nm E₁ ¹ =36

Max. at 272 nm E₁ ¹ =42

Max. at 277 nm E₁ ¹ =40

RMN Spectrum (deuterochloroform)

peaks at 1.19-1.33 ppm (hydrogens of geminal methyls); at 1.66-2.25 ppm(1- and 3-hydrogens of cyclopropane); 4.0-4.41 ppm (1'-hydrogen of3-ethyl of cyclopropane); at 5.18 ppm (methylene of benzyl); and at6.83-7.67 ppm (hydrogens of aromatic ring).

EXAMPLE 23 (S) allethrolone2,2-dimethyl-3R-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylate

The acid chloride prepared from 10.4 g of2,2-dimethyl-3R-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylicacid by the procedure of Step B of Example 21 was dissolved in 30 ml ofbenzene to obtain a final solution of 37.2 ml to which a solution of 3.2g of (S) allethrolone in 15 ml of benzene was added at 0° C. 2 ml ofpyridine were added thereto with stirring and the mixture was stirred at20° C. for 16 hours and was then poured into a mixture of water, ice andhydrochloric acid. The mixture was extracted with ether and the organicphase was evaporated to dryness under reduced pressure. The residue waschromatographed over silica gel and was eluted with a 8-1cyclohexane-ethyl acetate mixture to obtain 4.56 g of (S) allethrolone2,2-dimethyl-3R-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylatewith a melting point of 85° C.

Analysis: C₁₇ H₂₀ Cl₄ O₃ ; molecular weight=414.16 Calculated: %C: 49.3;%H: 4.8; %Cl: 34.2; Found: %C: 49.0; %H: 4.8; %Cl: 35.5.

I.R. Spectrum (chloroform)

Absorptions at 1710 and 1730 cm⁻¹ (carbonyl), at 1655 and 1538 cm⁻¹(C═C) and at 918 and 992 cm⁻¹ (--C═CH₂).

U.V. Spectrum (ethanol)

Max. at 227-228 nm E₁ ¹ =357

Max. at 278 nm E₁ ¹ =8

RMN Spectrum (deuterochloroform)

peaks at 1.32-1.37 ppm (hydrogens of geminal methyls); at 2.08 ppm(hydrogens of 2-methyl of allethrolone); at 2.98-3.08 ppm (hydrogens ofmethylene of allyl of allethrolone); at 4.12-4.23 and 4.28-4.39 ppm(1'-hydrogen of 3-ethyl of cyclopropane); at 4.83-5.25 ppm (terminalmethylene of allyl of allethrolone); and at 5.5 to 6.17 ppm (hydrogenattached to 1'-carbon of allethrolone and hydrogen of carbon β to allylchain of allethrolone).

EXAMPLE 24 3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate

4 ml of pyridine were progressively added at 0° C. to a solution of 4.65g of2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylicacid chloride and 2.40 g of 3-phenoxy-benzyl alcohol in 20 ml of benzeneand the mixture was stirred for 17 hours and was then poured intoaqueous hydrochloric acid. The mixture was extracted with benzene andthe organic phase was washed with a saturated aqueous sodium bicarbonatesolution, with water, dried over magnesium sulfate and evaporated todryness under reduced pressure. The residue was chromatographed oversilica gel and was eluted with a 9-1 petroleum ether (b.p.=35°-75°C.)-ethyl ether mixture to obtain 2.37 g of a mixture of the A and Bisomers of 3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylatemelting at 75° C.

Analysis: C₂₁ H₂₀ Br₂ Cl₂ O₃ ; molecular weight=551.11 Calculated: %C:45.76; %H: 3.65; %Br: 29.0; %Cl: 12.86; Found: %C: 45.8; %H: 3.6; %Br:28.5; %Cl: 12.9.

I.R. Spectrum (chloroform)

Absorption at 1725 cm⁻¹ (carbonyl) and at 1615, 1590 and 1492 cm⁻¹(aromatic ring).

RMN Spectrum (deuterochloroform)

peaks at 1.25-1.37 and 1.22-1.39 ppm (hydrogens of geminal methyls); at1.75-2.17 ppm (1- and 3-hydrogens of cyclopropane); at 5.1-5.16 ppm(hydrogens of methylene of benzyl); at 5.0-5.42 nd 5.35-5.53 ppm(1'-hydrogen of 3-ethyl of cyclopropane); and at 6.83-7.59 ppm(hydrogens of aromatic ring) RMN spectrum showed the product to be about1/3 of isomer B and about 2/3 of isomer A. The starting acid chloride,described in example 15 may also be prepared as in example 16 startingwith the 2,2-dimethyl3R-(2',2'-dichlorovinyl)-cyclopropane-1R-carboxylic acid.

EXAMPLE 25 (S) allethrolone2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate

A mixture of 2 ml of pyridine and 2 ml of benzene were added at 0° C. toa solution of 1.75 g of (S) allethrolone and 4 g of2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylicacid chloride prepared from 3.6 g of the corresponding acid by theprocess of Step B of Example 24 in 40 ml of benzene and the mixture wasstirred for 24 hours at 20° C. and was poured into a mixture ofwater-ice-hydrochloric acid. The mixture was extracted with benzene andthe organic phase was washed with an aqueous saturated sodiumbicarbonate solution and with water, dried over sodium sulfate andevaporated to dryness under reduced pressure to obtain 5.1 g of residuewhich was chromatographed over silica gel. Elution with a 97-3benzene-ethyl acetate mixture yielded 4.25 g of (S) allethrolone2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate.

Analysis: C₁₇ H₂₀ Br₂ Cl₂ O₃ ; molecular weight=503.07 Calculated: %C:40.58; %H: 4.0; %Br: 31.76; %Cl: 14.09; Found: %C: 41.3; %H: 4.1; %Br:31.0; %Cl: 14.2.

I.R. Spectrum (chloroform)

Absorption at 1718 cm⁻¹ (carbonyl), at 1655 and 1638 cm⁻¹ (C═C) and at918-997 cm⁻¹ (--CH═CH₂).

RMN Spectrum (deuterochloroform)

peaks at 1.25-1.28 and 1.39-1.42 ppm (hydrogens of geminal methyls); at1.95-2.07 ppm (hydrogens of 3'-methyl of allethrolone); at 4.83-6.17 ppm(hydrogens of terminal methylene of allyl of allethrolone); at 4.83-6.17ppm (1'-hydrogen of 3-ethyl of cyclopropane); and at 5.75 ppm(4'-hydrogen of allethrolone).

EXAMPLE 26 5-benzyl-3-furyl-methyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate

A solution of 2.9 g of 5-benzyl-3-furyl-methyl alcohol in 15 ml ofbenzene was added at 0° C. to 12 ml of a 27 ml solution of2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylicacid chloride prepared from 10 g of the corresponding acid in benzeneand then 3 ml of pyridine were added thereto. The mixture was stirredfor 48 hours at 20° C. and was then poured into a water-ice-hydrochloricacid mixture. The mixture was extracted with benzene and the benzeneextract was treated as before and evaporated to dryness. The residue waschromatographed over silica gel and was eluted with a 95-5 petroleumether (b.p.=35°-75° C.)-ether mixture and then a 9-1 petroleum ether(b.p.=35°-75° C.)-ether mixture to obtain 2.2 g of5-benzyl-3-furylmethyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)cyclopropane-1R-carboxylatewith a specific rotation [α]_(D) ²⁰ =-57.5° (c=0.4% in benzene).

Analysis: C₂₀ H₂₀ Br₂ Cl₂ O₃ ; molecular weight=539.104. Calculated: %C:44.56; %H: 3.74; %Br: 29.04; %Cl: 13.15; Found: %C: 44.9; %H: 3.8; %Br:29.1; %Cl: 13.3.

U.V. Spectrum (ethanol)

Inflex. at 252 nm E₁ ¹ =20

Inflex. at 258 nm E₁ ¹ =15

Inflex. at 264 nm E₁ ¹ =11

Inflex. at 268 nm E₁ ¹ =9

I.R. Spectrum (chloroform)

Absorption at 1720 cm⁻¹ (carbonyl) and at 1600, 1522 and 1493 cm⁻¹(aromatic ring).

RMN Spectrum (deuterochloroform)

peaks at 1.23-1.35 and 1.20-1.38 ppm (hydrogens of 2-methyls ofcyclopropane); at 1.67-2.17 ppm (1- and 3-hydrogens of cyclopropane); at3.93 ppm (hydrogens of methylene of benzyl); at 4.93-5.0 ppm (hydrogensof carbon attached to carboxyl); at 6.02-6.1 ppm (3-hydrogen of furan);at 4.83-5.16-5.33-5.58 ppm (1'-hydrogen of 3-ethyl of cyclopropane); at7.3 ppm (hydrogens of phenyl); and at 7.37 ppm (5-hydrogen of furan).

EXAMPLE 27 3,4,5,6-tetrahydrophthalimidomethyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate

The acid chloride prepared from 10 g of2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylicacid by the method of Example 24 was dissolved in benzene to obtain atotal volume of 27 ml and 7.5 ml of the said solution were added to asolution of 1.4 g of 3,4,5,6-tetrahydrophthalimidomethyl alcohol in 15ml of benzene. 2 ml of pyridine were added thereto at 0° C. and themixture was stirred for 36 hours at 20° C. and was poured into a mixtureof ice, water and hydrochloric acid. The mixture was extracted withbenzene and the organic phase was washed with an aqueous saturatedsodium bicarbonate solution, then with water, dried over sodium sulfateand evaporated to dryness under reduced pressure. The residue waschromatographed over silica gel and was eluted with a 9-1 benzene-ethylacetate mixture to obtain 1.89 g of 3,4,5,6-tetrahydrophthalimidomethyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylatewith a specific rotation of [α]_(D) ²⁰ =-53.5° (c=0.98% in benzene).

Analysis: C₁₇ H₁₉ Br₂ Cl₂ NO₄ ; molecular weight=532.07 Calculated: %C:38.37; %H: 3.6; %Br: 30.03; %Cl: 13.32; %N: 2.63; Found: %C: 39.0; %H:3.6; %Br: 28.3; %Cl: 12.7; %N: 2.6.

I.R. Spectrum (chloroform)

Absorptions at 1778, 1735 and 1723 cm⁻¹ (carbonyl) and at 1665 cm⁻¹(--C═C--).

RMN Spectrum (deuterochloroform)

peaks at 1.21-1.22-1.39 ppm (hydrogens of geminal methyls); at 1.67-1.83ppm (1- and 3-hydrogens of cyclopropane and methylenes α to --C═C--); at2.37 ppm (methylenes α to --C═C--); at 5.0-5.5 ppm (1'-hydrogen of3-ethyl of cyclopropane); and at 5.5-5.75 ppm (hydrogens of methylene αto carboxyl).

EXAMPLE 28 (R,S)α-cyano-3-phenoxy-benzyl dl cis-trans2,2-dimethyl-3-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1-carboxylate

The starting (R,S)α-cyano-3-phenoxy-benzyl dl-cis trans2,2-dimethyl-3-(2',2'-dichlorovinyl)-cyclopropane-1-carboxylate had thefollowing characteristics:

U.V. Spectrum (ethanol)

Inflex. at 226 nm E₁ ¹ =522

Inflex. at 267 nm E₁ ¹ =43

Inflex. at 272 nm E₁ ¹ =47

Max. at 278 nm E₁ ¹ =52

RMN Spectrum (deuterochloroform)

peaks at 1.20-1.30 ppm (hydrogens of methyl groups); at 5.60-5.75 ppm(1'-hydrogen of dichlorovinyl of trans isomer); at 6.20-6.31 ppm(1'-hydrogen of dichlorovinyl of cis isomer); at 6.41-6.46 ppm (hydrogenon carbon α to --CN); and at 7.0 to 7.66 ppm (hydrogens of aromaticring).

A solution of 0.85 ml of bromine in 10 ml of carbon tetrachloride wereadded over an hour to a solution of 6.7 g of the above indicated esterin 30 ml of carbon tetrachloride and the solution was stirred for 2hours at 20° C. and was concentrated to dryness under reduced pressure.The 10 g of residue was chromatographed over silica gel and was elutedwith a 9-1 cyclohexane-ethyl acetate mixture to obtain 7.5 g of(R,S)α-cyano-3-phenoxy-benzyl dl-cis trans2,2-dimethyl-3-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1-carboxylate.

Analysis: C₂₂ H₁₉ Br₂ Cl₂ NO₃ ; Calculated: %C: 45.86; %H: 3.32; %N:2.43; %Cl 12.30; %Br: 27.74; Found: %C: 46.2; %H: 3.6; %N: 2.4; %Cl:12.5; %Br: 27.5.

U.V. Spectrum (ethanol)

Inflex. at 267 nm E₁ ¹ =34

Inflex. at 272 nm E₁ ¹ =35

Max. at 277 nm E₁ ¹ =38

RMN Spectrum (deuterochloroform)

peaks at 1.20-1.44 ppm (hydrogens of methyls); at 1.54-2.40 ppm (1- and3-hydrogens of cyclopropane); at 4.21-4.51 ppm (1'-hydrogen ofdichlorovinyl of trans isomer); at 4.97 to 5.40 ppm (1'-hydrogen ofdichlorovinyl of cis isomer); at 6.42 to 6.50 ppm (hydrogen on carbon αto --CN); and at 7.0 to 7.55 ppm (hydrogens of aromatic ring).

EXAMPLE 29 5-benzyl-3-furyl-methyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate

5 ml of pyridine were added dropwise to a mixture of 30 ml of benzene,3.2 g of 5-benzyl-3-furyl-methanol and 7.6 g of2,2-dimethyl-3R-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylicacid chloride [prepared from the acid of Example 10 by the procedure ofExample 16] and the mixture was stirred for 48 hours at 20° C. Water wasadded thereto and the organic phase was decanted. The aqueous phase wasextracted with benzene and the combined organic phases were dried andevaporated to dryness under reduced pressure. The residue waschromatographed over silica gel and was eluted with a 7-3benzene-cyclohexane mixture to obtain 6.1 g of 5-benzyl-3-furyl-methyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylatewith a specific rotation of [α]_(D) ²⁰ =-19° (c=0.5% in benzene).

Analysis: C₂₀ H₂₀ Br₂ Cl₂ O₃ ; molecular weight=539.09 Calculated: %C:44.56; %H: 3.74; %Br: 29.65; %Cl: 13.15; Found: %C: 44.2; %H: 3.7; %Br:29.4; %Cl: 13.5.

I.R. Spectrum

Absorption at 1725 cm⁻¹ (carbonyl) and at 1555, 1540, 1498 and 1495 cm⁻¹(--C═C-- and aromatic ring).

U.V. Spectrum (ethanol)

Inflex. at 216 nm E₁ ¹ =265

Inflex. at 251 nm E₁ ¹ =10.5

Max. at 257 nm E₁ ¹ =8.5

Inflex. at 261 nm E₁ ¹ =7

Inflex. at 263 nm E₁ ¹ =6

Max. at 268 nm E₁ ¹ =4.5

RMN Spectrum (deuterochloroform)

peaks at 1.22-1.25-1.28 ppm (hydrogens of geminal methyls); at 1.6-2.32ppm (1- and 3-hydrogens of cyclopropane); 3.93 ppm (hydrogens ofmethylene of benzyl); at 4.25-4.37-4.54 ppm (1'-hydrogen of 3-ethyl ofcyclopropane); 4.95-4.97 ppm and 6.0-6.05 ppm (hydrogens of methylene αto carboxyl); at 7.33 ppm (4-hydrogen of furyl); and at 7.25 ppm(hydrogens of phenyl).

EXAMPLE 30 3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate

A solution of 19.35 g of2,2-dimethyl-3R-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylicacid chloride in benzene was added dropwise to a solution of 9 g of3-phenoxy-benzyl alcohol, 50 ml of benzene and 10 ml of pyridine and themixture was stirred at 20° C. for 18 hours and was then poured intowater. The mixture was extracted with benzene and the organic phase wasdried over magnesium sulfate and was evaporated to dryness. The residuewas chromatographed over silica gel and was eluted with a 95-5 petroleumether (b.p.=35°-75° C.)-ethyl ether mixture to obtain 8.1 g of3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylatewith a specific rotation of [α]_(D) ²⁰ =-20.5° (c=0.6% in benzene).

Analysis: C₂₁ H₂₀ Br₂ Cl₂ O₃ ; molecular weight=551.11 Calculated: %C:45.17; %H: 3.66; %Br 29.0; %Cl 12.87; Found: %C: 45.7; %H: 3.7; %Br28.5; %Cl 13.0.

I.R. Spectrum (chloroform)

Absorption at 1730 cm⁻¹ (carbonyl) and at 1618 and 1590 cm⁻¹ (aromaticring).

U.V. Spectrum (ethanol)

Inflex. at 228 nm E₁ ¹ =216

Inflex. at 267 nm E₁ ¹ =34

Max. at 272 nm E₁ ¹ =37.5

Max. at 278 nm E₁ ¹ =36

RMN Spectrum (deuterochloroform)

peaks at 1.22-1.27-1.29 ppm (hydrogens of geminal methyls); at 1.66-1.75ppm and 1.92-2.13 ppm (1-hydrogen of cyclopropane); at 1.92-2.33 ppm(3-hydrogen of cyclopropane); at 4.22-4.38 and 4.38-4.57 ppm(1'-hydrogen of 3-ethyl of cyclopropane); at 5.12-5.13 ppm (hydrogens ofmethylene of benzyl); and at 6.83-7.53 ppm (hydrogens of aromatic ring).

EXAMPLE 31 3,4,5,6-tetrahydrophthalimidomethyl2-dimethyl-3R-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate

2.5 ml of pyridine were added dropwise to a solution of 0.930 g of3,4,5,6-tetrahyrophthalimidomethyl alcohol and 2 g of2,2-dimethyl-3R-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylicacid chloride in 20 ml of benzene and the mixture was stirred for 48hours at 20° C. Water was added thereto and the mixture was extractedwith benzene. The combined organic phases were evaporated to dryness andthe residue was chromatographed over silica gel. Elution with a 9-1benzene-ethyl acetate mixture yielded 2.17 g of3,4,5,6-tetrahydrophthalimidomethyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylatemelting at 117° C. and having a specific rotation of [α]_(D) ²⁰ =-6.5°(c=0.9% in benzene).

Analysis: C₁₇ H₁₉ Br₂ Cl₂ NO₄ ; molecular weight=532.066 Calculated: %C;38.38; %H 3.60; %Br 30.04; %Cl 13.32; %N 2.63; Found: %C; 38.5; %H 3.5;%Br 29.9; %Cl 13.4; %N 2.5.

I.R. Spectrum (chloroform)

Absorption at 1783 cm⁻ (carbonyl); at 1728 and 1750 cm⁻¹ (carbonyl andester functions); and at 1669 cm⁻¹ (carbonyl).

U.V. Spectrum (ethanol)

Max. at 223 nm E₁ ¹ =301

Max. at 229-230 nm E₁ ¹ =293

Inflex. at 236 nm E₁ ¹ =172

Inflex. at 272 nm E₁ ¹ =8

EXAMPLE 32 3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylateSTEP A:2,2-dimethyl-3R-(1',2'-dichloro-2',2'-dibromoethyl)cyclopropane-1R-carboxylicacid

24 g of 2,2-dimethyl-3S-(2',2'-dibromovinyl)-cyclopropane-1R-carboxylicacid were added to a mixture of 20 ml of carbon tetrachloride and 20 mlof methylene chloride and chlorine was bubbled into the reaction mixtureat -10° C. provided in the reaction area with a refrigerant withmethanol circulating at -60° C. The mixture was stirred for 21/2 hoursat -10° C. and for 90 minutes at +10° C. and excess chlorine was allowedto evaporate. The mixture was evaporated to dryness under reducedpressure and the residue was chromatographed over silica gel. Elutionwith a 75-25-1 cyclohexane-ethyl acetate-acetic acid mixture yielded16.3 g of2,2-dimethyl-3R-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylicacid.

RMN Spectrum (deuterochloroform)

peaks at 1.33-1.56 ppm (hydrogens of geminal methyls); at 1.7-12.25 ppm(1- and 3-hydrogens of cyclopropane); at 4.11-4.37 ppm (1'-hydrogen of3-methyl of cyclopropane); and at 10.8 ppm (carboxyl hydrogen).

STEP B: 3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate

A solution of the acid chloride obtained from 4.5 g of2,2-dimethyl-3R-(1',2'-dichloro-2',2'-dichloroethyl)cyclopropane-1R-carboxylicacid prepared by Step B of Example 16 in 7 ml of benzene was added at 0°C. to a solution of 2.7 g of 3-phenoxy-benzyl alcohol in 7 ml of benzeneand 1.5 ml of pyridine was added thereto. The mixture was stirred for 16hours at 20° C. and was poured into a mixture of water, ice andhydrochloric acid. The mixture was extracted with ether and the organicphase was washed with water, dried over magnesium sulfate and evaporatedto dryness under reduced pressure. The 6.37 g of residue waschromatographed over silica gel and eluted with a 9-1 cyclohexane-ethylacetate mixture to obtain 2.09 g of 3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate.

Analysis: C₂₁ H₂₀ Cl₂ Br₂ O₃ ; molecular weight=551.12 Calculated: %C:45.7; %H 3.6; %Br 29; %Cl 12.8; Found: %C: 46.0; %H 3.8; %Br 29.4. 12.6;

I.R. Spectrum (chloroform)

Absorption at 1730 cm⁻¹ (carbonyl) and at 1615, 1590 cm⁻¹ (aromaticring).

U.V. Spectrum (ethanol)

Inflex. at 220 nm E₁ ¹ =205

Inflex. at 266 nm E₁ ¹ =33

Max. at 271-272 nm E₁ ¹ =36

Max. at 278 nm E₁ ¹ =34

RMN Spectrum (deuterochloroform)

peaks at 1.25-1.28-1.33 ppm (hydrogens of geminal methyls); at 1.72-2.42ppm (1- and 3-hydrogens of cyclopropane); at 3.98-4.35 ppm (1'-hydrogenof 3-ethyl of cyclopropane); 6.85-7.5 ppm (hydrogens of aromatic ring);and at 5.13 ppm (hydrogens of methylene of benzyl).

EXAMPLE 33 (S) allethrolone2,2-dimethyl-3R-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate

A solution of the acid chloride formed from 4.5 g of2,2-dimethyl-3R-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylicacid in 7 ml of benzene was added at 0° C. to a solution of 2.05 g of(S) allethrolone in 7 ml of benzene and 1.5 ml of pyridine were addedthereto. The mixture was stirred for 16 hours at 20° C. and was pouredinto a mixture of water, ice and hydrochloric acid. The mixture wasextracted with ether and the organic phase was washed with water, driedover magnesium sulfate and evaporated to dryness. The 5.15 g of residuewas chromatographed over silica gel and was eluted with a 4-1cyclohexane-ethyl acetate mixture to obtain 1.86 g of (S) allethrolone2,2-dimethyl-3R-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylatemelting at 126° C.

I.R. Spectrum (chloroform)

Absorption at 1713 and 1730 cm⁻¹ (carbonyl); at 1658 and 1642 cm⁻¹(--C═C--) and at 923 and 995 cm⁻¹ (--CH═CH₂).

U.V. Spectrum (ethanol)

Max. at 229 nm E₁ ¹ =315

Inflex. at 300 nm E₁ ¹ =1

RMN Spectrum (deuterochloroform)

peaks at 1.32-1.35-1.38 ppm (hydrogens of geminal methyls); at 4.23-4.4and 4.1-4.27 ppm (1'-hydrogen of 3-ethyl of cyclopropane); at 2.08-2.15ppm (hydrogens of 3-methyl of allethrolone); at 2.98-3.08 ppm(5-methylene of allethrolone); at 4.85-5.25 ppm (hydrogens of terminalmethylene of allethrolene); at 5.5-6.17 ppm (hydrogen β to allyl ofallethrolone); and at 5.83 (4'-hydrogen of allethrolone).

EXAMPLE 34 3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylateSTEP A:2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)cyclopropane-1R-carboxylicacid chloride

A mixture of 5 g of2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylicacid, 10 ml of thionyl chloride and 30 ml of petroleum ether(b.p.=35°-70° C.) was refluxed for 4 hours and was evaporated to drynessunder reduced pressure. The residue was added to benzene and thesolution was evaporated to dryness under reduced pressure to obtain 5.4g of2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylicacid chloride.

STEP B: 3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate

A solution of 4.35 g of pyridine in 10 ml of benzene was progressivelyadded at 8° C. to a mixture of 5.4 g of the acid chloride of Step A, 3.2g of 3-phenoxy-benzyl alcohol and 38 ml of benzene and the mixture wasstirred at 20° C. for 17 hours and was then poured into a mixture of iceand water. The mixture was extracted with benzene and the organic phasewas dried over magnesium sulfate and was evaporated to dryness. Theresidue was chromatographed over silica gel and was eluted with a 7-3benzene-ethyl acetate mixture to obtain a product which was crystallizedfrom petroleum ether (b.p.=35°-70° C.) to obtain 4.7 g of3-phenoxybenzyl2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)cyclopropane-1R-carboxylatemelting at 68° C. and having a specific rotation of [α]_(D) ²⁰ =-34°(c=1% chloroform).

Analysis: C₂₁ H₂₀ Cl₂ Br₂ O₃ ; molecular weight=551.20 Calculated: %C45.76 %H: 3.66; %Br: 29.00; %Cl: 12.86; Found: %C: 46.0 %H: 3.6; %Br29.3; %Cl: 12.7.

I.R. Spectrum (chloroform)

Absorption at 1725 cm⁻¹ (carbonyl) and at 1615, 1588 and 1490 cm⁻¹(aromatic ring).

U.V. Spectrum (ethanol)

Inflex. at 227 nm E₁ ¹ =214

Inflex. at 266 nm E₁ ¹ =33

Max. at 272 nm E₁ ¹ =35

Max. at 278 nm E₁ ¹ =36

RMN Spectrum (deuterochloroform)

peaks at 1.22-1.39 ppm and 1.26-1.42 ppm (hydrogens of geminalmethyls)at 1.66-2.08 ppm (1- and 3-hydrogens of cyclopropane); at 4.8-5.37 ppm(hydrogens of ##STR13## and at 6.83-7.58 ppm (hydrogens of aromaticring).

EXAMPLE 35 (S) allethrolone2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylateSTEP A:2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)cyclopropane-1R-carboxylicacid

A solution of 15.2 g of bromine in 40 ml of carbon tetrachloride wasadded over 2 hours at -65° C. to a solution of 17 g of2,2-dimethyl-3R-(2',2'-difluorovinyl)-cyclopropane-1R-carboxylic acid in120 ml of methylene chloride and the mixture was stirred for 21/2 hoursat -65° C. after which the temperature was allowed to return to roomtemperature. The mixture was evaporated to dryness under reducedpressure and the residue was dissolved in 50 ml of hot carbontetrachloride. The solution was cooled to 0° C. and was stirred at 0° C.for 45 minutes and was then filtered. The filtrate was evaporated todryness under reduced pressure and the residue was dissolved in 40 ml ofcarbon tetrachloride. The mixture was stirred at -10° C. for 30 minutesand was filtered. The filtrate was evaporated to dryness under reducedpressure and the residue was chromatographed over silica gel. Elutionwith a 3-1 cyclohexane-ethyl acetate mixture yielded a product which wascrystallized from petroleum ether (b.p.=35°-75° C.) to obtain 1.465 g of2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylicacid melting at 124° C.

RMN Spectrum (deuterochloroform)

peaks at 1.28-1.38 ppm (hydrogens of geminal methyls); at 1.67-2.0 ppm(1- and 3-hydrogens of cyclopropane); and at 4.67-5.33 ppm (1'-hydrogenof 3-ethyl of cyclopropane).

STEP B:2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)cyclopropane-1R-carboxylicacid chloride

A mixture of 2.5 ml of thionyl chloride, 1.43 g of the acid of Step Aand 15 ml of petroleum ether (b.p.=35°-75° C.) was refluxed for 41/2hours and then excess thionyl chloride was removed and the mixture wasevaporated to dryness under reduced pressure. The residue was taken upin benzene and the solution was evaporated to dryness under reducedpressure to obtain2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylicacid chloride which was used as is for the next step.

STEP C: (S) allethrolone2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylate

A solution of 0.7 g of (S) allethrolone in 5 ml of benzene was added at2° C. to a solution of the product of Step B in 10 ml of benzene andafter the addition of 0.5 ml of pyridine, the mixture was stirred for 16hours at 20° C. The mixture was poured into a water-ice-hydrochloricacid mixture and the mixture was extracted with ethyl ether. The organicphase was washed with water, dried over sodium sulfate and evaporated todryness to obtain 2.02 g of raw product. The latter was chromatographedover silica gel and was eluted with a 4-1 cyclohexane-ethyl acetatemixture to obtain 1.224 g of (S) allethrolone2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylate.

Analysis: C₁₇ H₂₀ Br₂ F₂ O₃ ; molecular weight=470.162 Calculated: %C:43.4; %H: 4.3; %Br: 34.0; %F 8.1; Found: %C: 43.2; %H: 4.4; %Br: 33.7;%F: 8.1.

U.V. Spectrum (ethanol)

Max. at 227-228 nm E₁ ¹ =348

RMN Spectrum (deuterochloroform)

peaks at 1.25-1.36 ppm (hydrogens of geminal methyls); at 2.02-2.06 ppm(hydrogens of 2-methyl of allethrolone); at 4.83-5.25 ppm (hydrogens ofterminal methylene of allyl of allethrolone); at 5.5-6.17 ppm (hydrogenβ to lateral chain of allethrolone and hydrogen of 1-carbon ofallethrolone); at 4.83-6.17 ppm (1'-hydrogen of 3-ethyl ofcyclopropane); at 1.67-2.16 ppm (1- and 3-hydrogens of cyclopropane); at2.95-3.05 ppm (hydrogens of methylene α- to side chain of allethrolone);and at 1.67-3.17 ppm (methylene of allethrolone ring).

EXAMPLE 36 (R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)cyclopropane-1R-carboxylateSTEP A:2,2-dimethyl-3S-(1',2'-dibromo-2,2'-difluoroethyl)cyclopropane-1R-carboxylicacid chloride

A mixture of 7 ml of thionyl chloride, 2.5 g of2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylicacid and 15 ml of petroleum ether (b.p.=35°-75° C.) was refluxed for131/2 hours and was evaporated to dryness under reduced pressure. Theresidue was taken up in benzene and the solution was evaporated todryness to obtain2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylicacid chloride which was used as is for the next step.

STEP B: (R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylate

A solution of 1.995 g of (R,S)α-cyano-3-phenoxybenzyl alcohol in 10 mlof benzene was added at 2° C. to a solution of the product of Step A in15 ml of benzene and after the addition of 1 ml of pyridine, the mixturewas stirred for 16 hours at 20° C. and was poured into awater-ice-hydrochloric acid mixture. The mixture was extracted withether and the organic phase was evaporated to dryness. The residue waschromatographed over silica gel and was eluted with a 9-1cyclohexane-ethyl acetate mixture to obtain 1.972 g of (R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylate.

Analysis: C₂₂ H₁₉ Br₂ F₂ NO₃ ; molecular weight=543.22 Calculated: %C:48.6; %H 3.5; %Br 29.4; %F: 7.0; %N; 2.6; Found: %C: 48.9; %H 3.5; %Br29.6; %F: 7.1; %N: 2.5.

I.R. Spectrum (chloroform)

Absorption at 1735 cm⁻¹ (carbonyl) and at 1588, 1610 and 1487 cm⁻¹(aromatic ring).

U.V. Spectrum (ethanol)

Inflex. at 230 nm E₁ ¹ =208

Inflex. at 268 nm E₁ ¹ =34

Inflex. at 273 nm E₁ ¹ =37

Max. at 278 nm E₁ ¹ =40

Inflex. at 285 nm E₁ ¹ =29

RMN Spectrum (deuterochloroform)

peaks at 1.03-1.45 ppm (hydrogens of geminal methyls); at 1.75-2.0 ppm(1- and 3-hydrogens of cyclopropane); at 4.42-5.17 ppm (1'-hydrogen of3-ethyl of cyclopropane); at 6.4-6.47 ppm (hydrogen α- to -CN); and at6.92-7.67 ppm (hydrogens of aromatic ring).

EXAMPLE 37 3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylateSTEP A:2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)cyclopropane-1R-carboxylicacid

A solution of 24 g of bromine in 50 ml of carbon tetrachloride was addedat -65° C. over 90 minutes to a solution of 26.4 g of2,2-dimethyl-3S-(2',2'-difluorovinyl)-cyclopropane-1R-carboxylic acid in150 ml of methylene chloride and the mixture was stirred at -60° C. for3 hours and was then allowed to return to 20° C. The mixture wasevaporated to dryness under reduced pressure and the residue wascrystallized from petroleum ether to obtain 14.09 g of2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylicacid melting at 116° C.

Analysis: C₈ H₁₀ Br₂ F₂ O₂ ; molecular weight=335.98 Calculated: %C:28.6; %H: 3.0; %BR: 47.6; %F: 11.3; Found: %C: 28.8; %H: 3.1; %Br: 47.7;%F: 11.5.

RMN Spectrum (deuterochloroform)

Peaks at 1.33 ppm (hydrogens of geminal methyls); at 1.5-2.33 ppm (1-and 3-hydrogens or cyclopropane); at 3.67-4.41 ppm (1'-hydrogen of3-ethyl of cyclopropane); and at 10.9 ppm (carboxyl hydrogen).

STEP B:2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)cyclopropane-1R-carboxylicacid chloride

A mixture of 10 ml of thionyl chloride, 11 g of2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylicacid and 40 ml of petroleum ether (b.p.=35°-75° C.) was refluxed for 4hours and after elimination of excess thionyl chloride, the mixture wasevaporated to dryness under reduced pressure. The residue ws taken up inbenzne and the solution was evaporated to dryness to obtain2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylicacid chloride which was used as is for the next step.

STEP C: 3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylate

The product of Step B was dissolved in 50 ml of benzene to obtain afinal solution of 56 ml and 18.5 ml thereof was added at 2° C. to asolution of 2.4 g of 3-phenoxybenzyl alcohol in 2.5 ml of benzene. 1 mlof pyridine was added thereto and the mixture was stirred at 20° C. for16 hours. The reaction mixture was poured into a water-ice-hydrochloricacid mixture and the mixture was extracted with ether. The organic phasewas washed with water, dried over magnesium sulfate and evaporated todryness. The residue was chromatographed over silica gel and was elutedwith a 95-5 cyclohexane-benzene mixture to obtain 3.204 g of3-phenoxybenzyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)cyclopropane-1R-carboxylate.

Analysis: C₂₁ H₂₀ Br₂ F₂ O₃ ; molecular weight=518.206 Calculated: %C:48.7; %H: 3.9; %Br: 30.9; %F: 7.3; Found: %C: 48.9 %H: 3.9; %BR: 31.0:%F: 7.1.

U.V. Spectrum (ethanol)

Inflex. at 225 nm E₁ ¹ =225

Inflex. at 265 nm E₁ ¹ =33

Max. at 271 nm E₁ ¹ =37

Max. at 277 nm E₁ ¹ =36

RMN Spectrum (deuterochloroform):

Peaks at 1.27 (hydrogens of geminal methyls); at 1.58-2.17 ppm (1- and3-hydrogens of cyclopropane); at 3.67-4.33 ppm (1'-hydrogen of 3-ethylof cyclopropane); at 5.13 ppm (methylene α-to carboxyl); and at7.58-7.75 ppm (hydrogens of aromatic ring).

EXAMPLE 38 (R,S,) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylate

11 g of2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylicacid was used to prepare the acid chloride thereof which was dissolvedin 50 ml of benzene and a solution of 5.4 ml of α-cyano-3-phenoxy-benzylalcohol in 5 ml of benzene was added at 0° C. to 37.5 ml of theresulting solution. 2 ml of pyridine were added thereto and the mixturewas stirred at 20° C. for 16 hours. The mixture was poured into awater-ice-hydrochloric acid mixture and the resulting mixture wasextracted with ether. The organic phase was treated as before andevaporated to dryness under reduced pressure. The residue waschromatographed over silica gel and was eluted with a 9-1cyclohexane-ethyl acetate mixture to obtain 5.46 g of(R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylate.

Analysis: C₂₂ H₁₉ Br₂ F₂ O₃ N; molecular weight=543.22 Calculated: %C:48.6; %H: 3.5; %Br: 29.4; %F: 7; %N: 2.6; Found: %C: 49.1; %H: 3.5; %Br:28.8; %F: 6.7; %N: 2.5.

I.R. Spectrum (chloroform)

Absorption at 1745 cm⁻¹ (carbonyl); at 1615-1590 cm⁻¹ (of aromaticring).

U.V. Spectrum (ethanol)

Inflex. at 230 nm E₁ ¹ =192

Inflex. at 269 nm E₁ ¹ =34

Inflex. at 273 nm E₁ ¹ =36

Max. at 278 nm E₁ ¹ =39

Inflex. at 305 nm E₁ ¹ =1

RMN Spectrum (deuterochloroform)

Peaks at 1.2-1.33 ppm (hydrogens of geminal methyls); at 1.9-2.25 ppm(1- and 3-hydrogens of cyclopropane); at 3.66-4.33 ppm (1'-hydrogen of3-ethyl of cyclopropane); at 6.45 ppm (hydrogen attached to same carbonas --CN); and at 6.91-7.58 ppm (hydrogens of aromatic ring).

EXAMPLE 39 A and Bisomers of 3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2'-chloro-2'(R,S)-fluoroethyl)-cyclopropane-1R-carboxylateSTEP A: 2,2-dimethyl-3S-(1',2'-dibromo-2'-chloro-2'-(R,S)fluoroethyl)-cyclopropane-1R-carboxylic acid

A solution of 2.4 ml of bromine in 20 ml of carbon tetrachloride wasadded at -10° C. over 30 minutes to a solution of 8.9 g of a mixture ofthe E and Z isomers of2,2-dimethyl-3R-(2'-chloro-2'-fluorovinyl)-cyclopropane-1R-carboxylicacid in 100 ml of carbon tetrachloride and the mixture was stirred at10° C. for 4 hours. The mixture was evaporated to dryness under reducedpressure and the residue was chromatographed over silica gel. Elutionwith ethyl acetate yielded 13.7 g of2,2-dimethyl-3S-(1',2'-dibromo-2'-(R,S)-fluoro-2'-chloroethyl)-cyclopropane-1R-carboxylicacid.

I.R. Spectrum (chloroform)

Absorption at 1710 cm⁻¹ (carbonyl) and 3510 cm⁻¹ (OH).

RMN (Spectrum (deuterochloroform)

Peaks at 1.30-1.32-1.42 ppm (hydrogens of geminal methyls); at 1.75-2.08ppm (1- and 3-hydrogens of cyclopropane); at 4.67-5.50 ppm (1'-hydrogenof 3-ethyl of cyclopropane); and at 10.75 ppm (carboxyl hydrogen).

STEP B: phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2'-(R,S)-fluoro-2'-chloroethyl)-cyclopropane-1R-carboxylate

A mixture of 3.5 g of the acid of Step A, 3.5 g of 3-phenoxy-benzylalcohol, 3.5 g of neopentyl acetal of dimethylformamide and 35 ml ofbenzene was heated for 17 hours at 50° C. and was then cooled andevaporated to dryness under reduced pressure. The residue waschromatographed over silica gel and was eluted with a 1-1benzene-cyclohexane mixture to obtain 1.050 g of the A isomer of3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2'-(R,S)-fluoro-2'-chloroethyl)-cyclopropane-1R-carboxylatemelting at 50° C.

Analysis: C₂₁ H₂₀ Br₂ ClFO₃ ; molecular weight=534.65 Calculated: %C:47.17; %H: 3.77; %BR: 29.89; %Cl: 6.63; %F: 3.55; Found: %C: 47.4; %H:3.8; %Br: 29.4; %Cl: 7.2; %F: 3.7.

I.R. Spectrum (chloroform)

Absorption at 1735 cm⁻¹ (carbonyl) and 1675, 1590 and 1490 cm⁻¹(aromatic ring).

RMN Spectrum (deuterochloroform)

Peaks at 1.23-1.39 ppm (hydrogens of geminal methyls); at 1.73-2.01 ppm(1- and 3-hydrogens of cyclopropane); at 5.08 ppm (hydrogens ofmethylene of benzyl); at 5.08-5.50 ppm (1'-hydrogen of 3-ethyl ofcyclopropane); and at 6.83-7.58 ppm (hydrogens of aromatic ring).

Also recovered were 0.62 g of the B isomer of the same ester having thefollowing charactertics:

Analysis:

Calculated: %C: 47.17; %H: 3.77; %Cl: 6.03; %F: 3.55; %Br: 29.89; Found:%C: 47.5; %H: 3.8; %Cl: 6.2; %F: 3.6; %Br: 29.6;

I.R. Spectrum (chloroform): identical to that of isomer A. RMN Spectrum(deuterochloroform)

Peaks at 1.22-1.34 ppm (hydrogens of geminal methyls); at 1.75-2.0 ppm(1- and 3-hydrogens of cyclopropane); at 5.12 ppm (hydrogens ofmethylene of benzyl); at 4.83-5.33 ppm (1'-hydrogen of 3-ethyl ofcyclopropane); and at 5.83-7.5 ppm (hydrogens of aromatic ring).

The starting acid was prepared by the procedure of Brown [thesis of 1974entitled Structure Activity Studies of Halopyrethroids published in 1976by Xerox University Microfilms, Ann Arbor., Michigan, p. 27 to 29] tomake the corresponding dl-trans acid but using tert.-butyl2,2-dimethyl-3S-formyl-cyclopropane-1R-carboxylate in place oftert.-butyl 2,2-dimethyl-3RS-formyl-cyclopropane-1RS-carboxylate.

EXAMPLE 40 3,4,5,6-tetrahydrophthalimidomethyl (1R, cis)2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylateSTEP A: (1R,cis)2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylicacid

19.4 g of (1R, cis)2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylic acid wereadded to 150 ml of carbon tetrachloric and then a solution of 10.4 g ofbromine in 22 ml of carbon tetrachloride was added thereto. The mixturewas stirred at 20° C. for one hour and was then concentrated to drynessunder reduced pressure to obtain 31.4 g of raw product melting at 145°C. The latter was crystallized from 110 ml of carbon tetrachloride toobtain 22.12 g of (1R, cis)2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylicacid melting at 150° C. which was a mixture of (A) and (B) isomers asdetermined by the RMN Spectrum.

The RMN Spectrum detected a compound corresponding to about 2/3 of themixture with peaks at 1.31 to 1.43 ppm (hydrogens of geminal methyls)and peaks at 5.33 to 5.66 ppm (hydrogen fixed to asymetrical monobromocarbon atom) and another compound corresponding to about 1/3 of themixture with peaks at 1.28-1.48 ppm (hydrogens of geminal methyls) andpeaks at 4.24 to 5.34 ppm (hydrogen fixed to asymetrical monobromocarbon atom). In the mixture, there were also peaks of 1.67 to 2.17 ppm(1- and 3-hydrogens of cyclopropane) and a peak towards 11.25 ppm(mobile hydrogen of acid function).

Analysis: C₈ H₁₀ Br₄ O₂ ; molecular weight=457.804 Calculated: %C:20.99; %H: 2.20; %Br: 69.82; Found: %C: 20.9; %H: 2.2; %Br: 70.2.

STEP B: (1R, cis)2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylicacid chloride

A mixture of 0.2 ml of dimethylformamide, 8.5 ml of thionyl chloride and179 ml of petroleum ether (b.p.=35°-75° C.) was heated to reflux and amixture of 35.76 g of the product of Step A in 150 ml of methylenechloride was added thereto. The mixture was refluxed with stirring for 2hours and was then cooled and evaporated to dryness. The residue wastaken up in toluene and the mixture was evaporated to dryness underreduced pressure to obtain 38 g of raw (1R,cis)2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylicacid chloride with a melting point of 88° C. which was used as is forthe next step.

STEP C: 3,4,5,6-tetrahydrophthalimidomethyl (1R, cis)2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylate

3 g of pyridine were added with stirring at 0° C. to a mixture of 7.7 gof the product of Step B, 2.9 g of neopynaminol and 50 ml of anhydrousbenzene and the temperature was permitted to return to room temperaturewith stirring over 18 hours. The mixture was poured into dilutehydrochloric acid and was then extracted with benzene. The organicextracts were washed with aqueous sodium bicarbonate solution and thenwith water until the wash water was neutral, dried over magnesiumsulfate and was filtered. The filtrate was evaporated to dryness underreduced pressure to obtain 10 g of raw product which was chromatographedover silica gel. Elution with a 95-5 benzene-ethyl acetate mixtureyielded 3.3 g 3,4,5,6-tetrahydrophthalimidomethyl (1R, cis)2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylatein the form of a mixture of its A and B isomers and 0.5 g of the saidproduct in its B isomer form.

A and B isomer mixture

Specific rotation of [α]_(D) ²⁰ =-21.5°±1° (c=1% in benzene)

Analysis: C₁₇ H₁₉ Br₄ NO₄ ; molecular weight=620.982 Calculated: %C:32.88; %H: 3.08; %N: 2.25; %Br: 51.47; Found: %C: 33.8; %H: 3.2; %N:2.1; %Br: 50.2.

U.V. Spectrum (ethanol)

Inflex. towards 218 nm E₁ ¹ =243

Max. at 223 nm E₁ ¹ =275; ε=17,100

Max. at 229 nm E₁ ¹ =269; ε=16,700

Inflex. towards 238 nm E₁ ¹ =170; ε=10,500

Inflex. towards 295 nm E₁ ¹ =8

RMN Spectrum (deuterochloroform)

Peaks at 4.98-5.17 ppm (1'-hydrogen of ethyl side chain of B isomer); at1.2-1.45 ppm (hydrogens of geminal methyls of B isomer); at 5.17-5.38ppm (1'-hydrogen of ethyl side chain of A isomer); 1.2-1.38 ppm(hydrogens of geminal methyls of A isomer); at 1.58-2.08 ppm (hydrogensof cyclopropyl and methylenes of cyclohexyl); massive at 2.33 ppm(hydrogens of methylenes of cyclohexyl); and peaks at 5.33-5.70 ppm(hydrogens of --COOCH₂ N--).

B isomer

Specific rotation of [α]_(D) ²⁰ =+72.5°±2.5° (c=0.5% in benzene)

Analysis: C₁₇ H₁₉ Br₄ NO₄ ; molecular weight=620.982 Calculated: %C:32.88; %H: 3.08; %N: 2.25; %BR: 51.47; Found: %C: 33.5; %H: 3.3; %N:2.2; %BR: 50.1.

U.V. Spectrum (ethanol)

Inflex. towards 218 nm E₁ ¹ =248

Max. at 223 nm E₁ ¹ =278

Max. at 228-229 nm E₁ ¹ =272

Inflex. towards 238 nm E₁ ¹ =172

Inflex. towards 295 nm E₁ ¹ =7

RMN Spectrum (deuterochloroform)

Peaks at 4.98-5.16 ppm (1'-hydrogen of ethyl side chain); 1.21-1.45 ppm(hydrogens of geminal methyls); 1.5-2 ppm (hydrogens of cyclopropyl andβ-methylenes of cyclohexyl); massive at 2.38 ppm (hydrogens ofmethylenes of cyclohexyl); and peaks at 5.38-5.57 and 5.57-5.75 p.p.m.(hydrogens of COOCH₂ N--).

EXAMPLE 41 3,4,5,6-tetrahydrophthalimidomethyl (1R, trans)2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylateSTEP A: (1R, trans)2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylicacid

Using the procedure of Step A of Example 40, (1R, trans)2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylic acid wasbrominated to obtain a mixture of the A and B isomers of (1R, trans)2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylicacid.

RMN Spectrum

Peaks at 1.30 to 1.40 ppm (hydrogens of geminal methyls of cyclopropyl);at 1.65-1.74 and 1.97 to 2.37 ppm (1- and 3 hydrogens of cyclopropyl);at 4.30-4.47 and 4.47-4.65 ppm (1'-hydrogen of 1'-ethyl); at 9.63 ppm(hydrogen of carboxyl).

STEP B: (1R, trans)2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylicacid chloride

Using the procedure of Step B of Example 40, the product of Step A wasreacted with thionyl chloride to obtain (1R, trans)2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylicacid chloride which was used as is for the next step.

I.R. Spectrum (chloroform): absorption at 1778 cm⁻¹

STEP C: 3,4,5,6-tetrahydrophthalimidomethyl (1R, trans)2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylate

Using the procedure of Step C of Example 40 7.7 g of the product of StepB were reacted to obtain 9.2 g of raw product which was chromatographedover silica gel. Elution was effected with a 9-1 benzene-ethyl acetatemixture and the product was taken up in petroleum ether (b.p.=40°-70°C.). The mixture was vacuum filtered and the product was dried to obtain5.4 g of a mixture of A and B isomers of3,4,5,6-tetrahydrophthalimidomethyl (1R, trans) 2,2-dimethyl-3-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1-carboxylate melting at 124° C.and having a specific rotation of [α]_(D) ²⁰ =-1°±1° (c=1% in benzene).

Analysis: C₁₇ H₁₉ Br₄ NO₄ ; molecular weight=620.982 Calculated: %C:32.88; %H: 3.08; %Br 51.47; %N: 2.25; Found: %C: 33.1; %H: 3.2; %Br51.1; %N: 2.1.

U.V. Spectrum (ethanol)

Max. at 224 nm E₁ ¹ =274; ε=17,000

Max. at 228 nm E₁ ¹ =269; ε=16,700

Inflex towards 235 nm E₁ ¹ =167; ε=10,400

Inflex. towards 280 nm E₁ ¹ =9

RMN Spectrum (deuterochloroform)

Peaks at 1.25-1.30-1.31 ppm (hydrogens of geminal methyls); at 1.58 to2.16 ppm (hydrogens of cyclopropyl and β-methylenes of cyclohexyl); at2.16 to 2.5 ppm (hydrogens of α-methylenes of cyclohexyl); at 4.24-4.41and 4.43-4.61 ppm (1'-hydrogen in 1'-position of ethyl side chain); at5.51 and 5.55 ppm (--COOCH₂ --N--)

EXAMPLE 42 (S) α-cyano-3-phenoxy-benzyl (1R, trans)2,2-dimethyl-3-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1-carboxylateSTEP A: (1R, trans)2,2-dimethyl-3-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1-carboxylicacid

Using the procedure of Step A of Example 40, (1R, trans)2,2-dimethyl-3-(2',2'-dichlorovinyl)-cyclopropane-1-carboxylic acid wasreacted with bromine to obtain a mixture of the (A) and (B) isomers of(1R, trans)2,2-dimethyl-3-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1-carboxylicacid.

RMN Spectrum

Peaks at 1.17-1.37 ppm (hydrogens of geminal methyls of cyclopropyl); at1.65-1.73 and 1.93-2.03 ppm (hydrogens in 1-position of cyclopropane);at 4.23-4.45 and 4.45-4.62 ppm (hydrogens of 1'-ethyl in the 3-positionof cyclopropane).

STEP B: (1R, trans)2,2-dimethyl-3-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1-carboxylicacid chloride

Using the procedure of Step B of Example 40, the product of Step A wasreacted with thionyl chloride to obtain (1R, trans)2,2-dimethyl-3-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1-carboxylicacid chloride.

I.R. Spectrum (chloroform): absorption at 1777 cm⁻¹ STEP C: Mixture of(1R, 5S) 6,6-dimethyl-4(R) [(S)cyano-(3'-phenoxyphenyl)-methoxy]-3-oxa-bicyclo-(3,1,0)-hexan-2-one and(1R, 5S) 6,6-dimethyl-4(R)-[(R)cyano-(3'-phenoxyphenyl)-methoxy]-3-oxa-bicyclo-(3,1,0)-hexan-2-one

A mixture of 22.5 g of (R,S) α-cyano-3-phenoxy-benzyl alcohol, 9.46 g ofthe lactone of (1R, 3S) cis2,2-dimethyl-3-dihydroxymethyl-cyclopropane-1-carboxylic acid and 0.150g of p-toluene sulfonic acid monohydrate was heated at 80° C. under areduced pressure of 10⁻² mm Hg for 2 hours and the water of reaction wasremoved by distillation. The mixture was cooled to 20° C. to obtain 30.7g of a raw mixture A of (1R, 5S) 6,6-dimethyl-(4R)-[(S)cyano-(3'-phenoxyphenyl)-methoxy]-3-oxa-bicyclo-(3,1,0)-hexan-2-one and(1R, 5S) 6,6-dimethyl-4R-[(R)cyano-(3'-phenoxyphenyl)-methoxy]-3-oxa-bicyclo-(3,1,0)-hexan-2-onecontaining the unreacted starting material as the principal impurity.

STEP D: (1R, 5S)6,6-dimethyl-4(R)-[(S)-cyano-(3'-phenoxyphenyl)-methoxy]-3-oxa-bicyclo-(3,1,0)-hexan-2-one

Mixture A of Step C was chromatographed over silica gel and was elutedwith a 95-5 benzene-ethyl acetate mixture to obtain 10.9 g of (1R, 5S)6,6-dimethyl-4(R)-[(S)-cyano-(3'-phenoxyphenyl)-methoxy]-3-oxa-bicyclo-(3,1,0)-hexan-2are melting at 126° C. and having a specific rotation of [α]_(D) ²⁰=-71° (c=1% in benzene).

STEP E: (S) α-cyano-3-phenoxy-benzyl alcohol

A mixture of 10 g of the product of Step D, 1 g of p-toluene sulfonicacid monohydrate, 100 ml of dioxane and 50 ml of water was refluxed for23 hours and was then evaporated under reduced pressure while addingether to the initial volume. The mixture was stirred and decanted andthe organic phase was washed with water, dried and evaporated to drynessunder reduced pressure. The 9.5 g of residue was chromatographed oversilica gel and was eluted with a 9-1 benzene-ethyl acetate mixture toobtain 6.1 g of (S) α-cyano-3-phenoxy-benzyl alcohol with a specificrotation of [α]_(D) ²⁰ =-16.5°±1.5° (c=0.8% in benzene).

RMN Spectrum (deuterochloroform)

Peak at 3.25 ppm (hydrogen of alcohol group); at 5.42 ppm (hydrogen ofcarbon with nitrile attached thereto).

STEP F: (S) α-cyano-3-phenoxy-benzyl (1R, trans)2,2-dimethyl-3-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1-carboxylate

A mixture of 4.45 g of the product of Step B, 2.6 g of (S)α-cyano-3-phenoxy-benzyl alcohol and 100 ml of anhydrous benzene wascooled to 15° C. and a solution of 5 ml of pyridine in 20 ml ofanhydrous benzene was added thereto. The mixture was stirred for 3 hoursat room temperature and was then poured into 100 ml of 2 N hydrochloricacid. The organic phase was washed with water and evaporated to drynessunder reduced pressure. The residue was chromatographed over silica geland was eluted with benzene to obtain 4.9 g of a mixture of the (A) and(B) isomers of (S) α-cyano-3-phenoxy-benzyl (1R, trans)2,2-dimethyl-3-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1-carboxylatewith a specific rotation of [α]_(D) ²⁰ =0° (c=1% in benzene).

Analysis: C₂₂ H₁₉ Cl₂ O₃ N; molecular weight=576.12 Calculated: %C:45.86; %H: 3.32; %Br: 27.74; %Cl: 12.31; %N: 2.43; Found: %C: 46.0; %H3.4; %Br: 27.5; %Cl: 12.2; %N: 2.2.

Circular dichroism

Max. at 287 nm Δ.sup.ε =+0.12

Max. at 282 nm Δ.sup.ε =+0.11

Max. at 265 nm Δ.sup.ε =+0.042

RMN Spectrum

Peaks at 1.20-1.26-1.31 ppm (hydrogens of geminal methyls); at 4.20-4.35and at 4.36-4.52 ppm (1'-hydrogen of ethyl side chain); at 1.68 to 1.78,1.97 to 2.07 and 1.97 to 2.42 ppm (hydrogens of cyclopropyl); at 6.42ppm (hydrogen of --COOCHCN); and at 6.92 to 7.58 ppm (hydrogens ofaromatic ring).

STEP G: Separation of isomers

4.69 g of the mixture of Step F were chromatographed over silica gel andwas eluted with a 30-12-0.4-1.2-0.03hexane-pentane-ether-acetonitrile-isopropanol mixture to obtain 1.385 gof isomer A of (S) α-cyano-3-phenoxy-benzyl (1R, trans)2,2-dimethyl-3-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1-carboxylatewith a specific rotation of [α]_(D) ²⁰ =+35.5°±2.5° (c=0.5% in benzene)and 0.980 g of the B isomer of the said ester with a specific rotationof [α]_(D) ²⁰ =-17.5°±2° (c=0.8% in benzene).

EXAMPLE 43 (S) α-cyano-3-phenoxy-benzyl (1R, cis)2,2-dimethyl-3-(2',2'-dibromo-1',2'-dichloroethyl)-cyclopropane-1-carboxylateSTEP A: (1R, cis)2,2-dimethyl-3-(2',2'-dibromo-1',2'-dichloroethyl)-cyclopropane-1-carboxylicacid

11.8 g of chlorine were bubbled into 30 ml of carbon tetrachloride at-15° C. and then a solution of 24 g of (1R, cis)2,2-dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-1-carboxylic acid in 37ml of methylene chloride was slowly added thereto at -10° C. The mixturewas stirred at 0° C. for 90 minutes and then at 25° C. for 2 hours andwas then evaporated to dryness under reduced pressure. The residue wascrystallized from carbon tetrachloride to obtain 7.4 g of a mixture ofthe (A) and (B) isomers of (1R, cis)2,2-dimethyl-3-(2',2'-dibromo-1',2'-dichloroethyl)-cyclopropane-1-carboxylicacid melting at 134° C.

RMN Spectrum

Peaks at 1.32-1.44 and 1.28-1.48 ppm (hydrogens of geminal methyls ofcyclopropane), at 5.08-5.45 and 4.67-5.0 ppm (1'-hydrogen of ethyl sidechain); at 10.1 ppm (carboxyl hydrogen).

STEP B: (1R, cis)2,2-dimethyl-3-(2',2'-dibromo-1',2'-dichloroethyl)-cyclopropane-1-carboxylicacid chloride

Using the procedure of Step B of Example 40, the product of Step A wasreacted with thionyl chloride to obtain (1R, cis)2,2-dimethyl-3-(2',2'-dibromo-1',2'-dichloroethyl)-cyclopropane-1-carboxylicacid chloride which was used as is for the next step.

STEP C: (S) α-cyano-3-phenoxy-benzyl (1R, cis)2,2-dimethyl-3-(2',2'-dibromo-1',2'-dichloroethyl)-cyclopropane-1-carboxylate

A solution of 4 ml of pyridine in 20 ml of anhydrous benzene was addedat 15° C. to a mixture of 3.8 g of the product of Step B, 2.5 g of (S)α-cyano-3-phenoxy-benzyl alcohol and 100 ml of anhydrous benzene and themixture was stirred at room temperature for 4 hours and was then pouredinto 100 ml of 2 N hydrochloric acid. The organic phase was washed withwater, dried and evaporated to dryness under reduced pressure. Theresidue was chromatographed over silica gel and was eluted with a 10-2petroleum ether (b.p.=40°-70° C.)-isopropyl ether mixture to obtain 1.8g of the (A) isomer of (S) α-cyano-3-phenoxy-benzyl (1R, cis)2,2-dimethyl-3-(2',2'-dibromo-1',2'-dichloroethyl)-cyclopropane-1-carboxylatewith Rf=0.30 and a specific rotation of [α]_(D) ²⁰ =-21°±1° (c=1% inbenzene) and 1.4 g of the (B) isomer of the said ester with an Rf=0.25and a specific rotation of [α]_(D) ²⁰ =+80°±2.5° (c=1% in benzene).

    ______________________________________                                        Circular Dichroism - isomer A                                                 ______________________________________                                        Max. at 300 nm       Δ.sup.ε = -0.003                           Max. at 288 nm       Δ.sup.ε = +0.29                            Max. at 264 nm       Δ.sup.ε = +0.11                            Max. at 232 nm       Δ.sup.ε = -1.8                             ______________________________________                                    

RMN Spectrum (deuterochloroform)--isomer A

Peaks at 1.28-1.37 ppm (hydrogens of geminal methyls); at5.05-5.10-5.18-5.23 ppm (1'-hydrogen of ethyl side chain); at 1.83-2.10ppm (hydrogens of cyclopropyl); at 6.38 ppm (hydrogen of --COOCHCN); at6.92 to 7.55 ppm (hydrogens of aromatic ring).

    ______________________________________                                        Circular Dichroism - isomer B:                                                ______________________________________                                        Max. at 288 nm        Δ.sup.ε = +0.22                           Inflex. towards 263 nm                                                                              Δ.sup.ε = +0.62                           Max. at 220 nm        Δ.sup.ε = +3.7                            ______________________________________                                    

RMN Spectrum (deuterochloroform)--isomer B

Peaks at 1.23-1.38 ppm (hydrogens of geminal methyls); at 4.6 to 4.95ppm (1'-hydrogen of ethyl side chain); at 1.75 to 2.16 ppm (hydrogens ofcyclopropyl); at 6.38 ppm (hydrogen of --COOCHCN); at 6.88 to 7.57 ppm(hydrogens of aromatic ring).

EXAMPLE 44 (S) α-cyano-3-phenoxy-benzyl (1R, cis)2,2-dimethyl-3-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1-carboxylateSTEP A: (1R, cis)2,2-dimethyl-3-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1-carboxylicacid

11.8 g of chlorine were dissolved in 30 ml of carbon tetrachloride and asolution of 16.7 g of (1R, cis)2,2-dimethyl-3-(2',2'-dichlorovinyl)-cyclopropane-1-carboxylic acid in40 ml of methylene chloride was added thereto at 0° C. over 30 minutes.The mixture was stirred at 0° C. for 24 hours and the temperature wasraised to 25° C. The mixture was stirred at 25° C. for 3 hours andexcess chlorine was removed by bubbling nitrogen through the mixture.The mixture was evaporated to dryness under reduced pressure and theresidue was chromatographed over silica gel. The product was eluted withan 8-2 cyclohexane-ethyl acetate mixture and was crystallized frompetroleum ether (b.p.=35°-75° C.) to obtain 3.14 g of (1R, cis)2,2-dimethyl-3-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1-carboxylicacid melting at 144° C.

Analysis: C₈ H₁₀ Cl₄ O₂ ; molecular weight=279.98 Calculated: %C: 34.3;%H: 3.6; %Cl: 50.6; Found: %C: 34.4; %H: 3.7; %Cl: 50.3.

RMN Spectrum (deuterochloroform)

Peaks at 1.26-1.42 ppm and 1.30-1.42 ppm (hydrogens of geminal methyls);at 4.67-5.17 ppm and 5.08 to 5.43 ppm (1'-hydrogen of ethyl side chain);at 1.67 to 2.0 ppm (hydrogens of cyclopropyl); at 10.2 ppm (hydroxyl ofcarboxyl).

STEP B: (1R, cis)2,2-dimethyl-3-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1-carboxylicacid chloride

6.75 g of the product of Step A were added to a mixture of 8.7 ml ofthionyl chloride and 60 ml of petroleum ether (b.p.=35°-70° C.) and themixture was refluxed for 41/2 hours and was then evaporated to drynessunder reduced pressure. The residue was taken up in benzene and themixture was evaporated to dryness to obtain raw (1R, cis)2,2-dimethyl-3-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1-carboxylicacid chloride which was used as is for the next step.

STEP C: (S) α-cyano-3-phenoxy-benzyl (1R, cis)2,2-dimethyl-3-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1-carboxylate

3 ml of pyridine were slowly added to a mixture of 3.19 g of the productof Step B, 2.6 g of (S) α-cyano-3-phenoxy-benzylalcohol and 30 ml ofanhydrous benzene cooled in an ice bath and the mixture was stirred for24 hours at room temperature and was then poured into cold dilutehydrochloric acid. The mixture was extracted with benzene and theorganic phase was washed with aqueous sodium bicarbonate solution, thenwith water, dried over sodium sulfate and filtered. The filtrate wasevaporated to dryness under reduced pressure and the residue waschromatographed over silica gel. Elution with a 7-3 benzene-cyclohexanemixture yielded 2.258 g of the (A) isomer of (S)α-cyano-3-phenoxy-benzyl (1R, cis)2,2-dimethyl-3-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1-carboxylatewith a specific rotation of [α]_(D) ²⁰ =+35.5°±2° (c=0.6% in benzene)and 1.48 g of a mixture of the (A) and (B) isomers of the said esterwith a specific rotation of [α]_(D) ²⁰ =-33.5°±2.5° (c=0.4% in benzene).

Analysis: C₂₂ H₁₉ Cl₄ NO₃ ; molecular weight=487.213 Calculated: %C:54.23; %H: 3.93; %N: 2.87; %Cl: 29.1; A isomer Found: %C: 54.4; %H: 3.8;%N: 2.8; %Cl: 28.5; A & B isomer Found: %C: 54.5; %H: 3.9; %N: 2.8; %Cl:28.8.

RMN Spectrum (deuterochloroform)--(A) isomer

Peaks at 1.28-1.37 ppm (hydrogens of geminal methyls); at 1.75 to 2.08ppm (hydrogens of cyclopropyl); at 5.07 to 5.25 ppm (1'-hydrogen ofethyl side chain); at 6.35 ppm (hydrogens of --COOCHCN); at 6.92 to 7.58ppm (hydrogens of aromatic ring).

RMN Spectrum (deuterochloroform)-(A) and (B) isomer mixture

Peaks at 1.2-1.35 ppm (hydrogens of geminal methyls of R isomer); at1.27-1.35 ppm (hydrogens of geminal methyls of isomer S); at 1.75-2.08ppm (hydrogens of cyclopropyl); at 4.77 to 4.94 ppm (1'-hydrogen ofethyl side chain); at 5.08 to 5.26 ppm (1'-hydrogen of ethyl sidechain); at 6.35 to 6.37 ppm (hydrogen of --COOCHCN); at 7.93 to 7.58 ppm(hydrogens of aromatic ring).

EXAMPLE 45 (R) α-cyano-3-phenoxy-benzyl (1R, trans)2,2-dimethyl-3-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1-carboxylateSTEP A: (R) α-cyano-3-phenoxybenzyl alcohol

The mixture of Step C of Example 42 was chromatographed to obtain 7.32 gof (1R, 5S)6,6-dimethyl-4(R)-[(R)-cyano-(3'-phenoxy-phenyl)-methoxy]-3-oxa-bicyclo-(3,1,0)-hexan-2-onewith a specific rotation of [α]_(D) ²⁰ =-120°±2.5° (c=0.9% in benzene).12.8 g of the said product were reacted as in Step E of Example 42 toobtain after chromatographic purification 5 g of (R)α-cyano-3-phenoxybenzyl alcohol with a specific rotation of [α]_(D) ²⁰=11°±2° (c±0.5% in benzene).

STEP B: (R) α-cyano-3-phenoxy-benzyl (1R, trans)2,2-dimethyl-3-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1-carboxylate

Using the procedure of Step F of Example 42, 2 g of (1R, trans)2,2-dimethyl-3-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1-carboxylicacid chloride and 1.1 g of (R) α-cyano-3-phenoxybenzyl alcohol werereacted to obtain 1.4 g of a mixture of the (A) and (B) isomers of (R)α-cyano-3-phenoxybenzyl (1R, trans)2,2-dimethyl-3-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1-carboxylatewith a specific rotation of [α]_(D) ²⁰ =-28°±2° (c=0.7% in benzene.

Analysis: C₂₂ H₁₉ Br₂ Cl₂ NO₃ ; molecular weight=576.122 Calculated: %C:45.87; %H: 3.32; %N 2.43; %Cl: 12.31; %Br: 27.74; Found: %C: 46.3; %H:3.3; %N: 2.4; %Cl: 12.4; %Br: 27.4.

RMN Spectrum (deuterochloroform)

Peaks at 1.31-1.35 ppm (hydrogens of geminal methyls); at 1.66 to 2.42ppm (hydrogens of cyclopropyl); at 4.23-4.42 ppm and 4.42-4.58 ppm(1'-hydrogen of ethyl side chain); at 6.47 ppm (hydrogen of --COOCHCN);at 6.92 to 7.58 ppm (hydrogens of aromatic ring).

Circular Dichroism (dioxane)

Max. at 219 nm ε=-5.4

Max. at 280 nm ε=-0.28

Inflex. towards 285 nm ε=-0.27

The mixture of A and B isomers was chromatographed over silical gel andwas eluted with a 7-2.8-0.17 hexane-pentane-ether mixture to separatethe A and B isomers.

RMN Spectrum (deuterochloroform): isomer A

Peaks at 1.32-1.37 ppm (hydrogens of geminal methyls); at 1.66-1.76 ppmand 2.08-2.17 ppm and 2.26-2.35 ppm (hydrogens of cyclopropyl); at4.2-4.37 ppm (1'-hydrogen of ethyl side chain); at 6.42 ppm (hydrogen of--COOCHCN); at 6.92 to 7.58 ppm (hydrogens of aromatic ring).

RMN Spectrum (deuterochloroform): isomer B

Peaks at 4.37-4.53 (1'-hydrogen of ethyl side chain).

EXAMPLE 46

An emulsifiable concentrate was prepared in the form of a homogeneousmixture of 0.25 g of the A isomer of (S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate,1 g of piperonyl butoxide, 0.25 g of Tween80, (polyoxyethylenederivative partial esters of fatty acids) 0.1 g of Topanol A and 98.4 gof water.

Another emulsifiable concentrate was prepared containing 0.015 g of thesame said A isomer or of (S) α-cyano-3-phenoxy-benzyl (1R, trans)2,2-dimethyl-3-(1';2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1-carboxylate, 0.5 g of piperonylbutoxide, 0.1 g of Topanol A and 99.385 g of xylene. A thirdemulsifiable concentrate was prepared containing 1.5 g of the same saidA isomer or of (S) α-cyano-3-phenoxy-benzyl (1R, trans)2,2-dimethyl-3-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1-carboxylate,20 g of Tween 80, 0.1 g of Topanol A and 78.4 g of xylene.

EXAMPLE 47

A fumigant composition was prepared comprising 0.25 g of the A isomer of(S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate,25 g of tabu powder, 40 g of cedar leaf powder, 33.75 g of pine sawdust,0.5 g of brilliant green and 0.5 g of p-nitrophenol.

EXAMPLE 48

An insecticide composition was prepared from 1 g of (R,S)α-cyano-3-phenoxy-benzyl dl cis-trans2,2-dimethyl-3-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1-carboxylate,8 g of piperonyl butoxide, 1 g of Tween 80, 0.1 g of Topanol A and 89.9g of water.

EXAMPLE 49

An emulsifiable concentrate useful as an acaricide was prepared from 20parts by weight of (S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylateor of (S) α-cyano-3-phenoxy-benzyl 1R, trans2,2-dimethyl-3-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1-carboxylate,6.5 parts by weight of Atlox 4851 (oxyethylene triglyceride with asulfonate-acid index of 1.5), 3.3 parts by weight of Atlox 4855(oxyethylene triglyceride with a sulfonate-acid index of 3) and 70.2parts by weight of xylene.

EXAMPLE 50

A nematocidal composition in the form of an emulisifiable concentratefor the treatment of soil contained, by weight, 45 parts of (S)α-cyano-3-phenoxy-benzyl-2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylateor of (S) α-cyano-3-phenoxy-benzyl (1R, trans)2,2-dimethyl-3-(2',2'-dichloro 1',2'-dibromoethyl)cyclopropane-1-carboxylate, 6.4 parts of Atlox 4851, 3.2 parts of Atlox4855 and 45.4 parts of xylene.

EXAMPLE 51

An ixodicide composition was prepared from 0.5 g of an equimolar mixtureof the A and B isomers of (S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylateor of (S) α-cyano-3-phenoxy benzyl (1R, trans)2,2-dimethyl-3(2',2'-dichloro 1',2'-dibromo ethyl)cyclopropane-1-carboxylate, 25 g of Triton X100, 10 g of Polysorbate 80,1 g of α-tocopherol acetate and sufficient ethanol for 100 ml ofmixture. The composition after dilution with 50 volumes of water wasused externally.

An injectable ixodicide composition was prepared from 2 g of anequimolar mixture of the A and B isomers of (S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylateor of (S) α-cyano-3-phenoxy benzyle (1R, trans)2,2-dimethyl-3-(2',2'-dichloro 1',2'-dibromoethyl)cyclopropane-1-carboxylate, 6.65 g of piperonyl butoxide, 0.33 g ofα-tocopherol acetate and sufficient oily excipient to obtain a finalvolume of 100 ml. The oily excipient was 29 g of benzyl benzoate inarachide oil for a final volume of 100 ml.

EXAMPLE 52

A feed base containing a minimum of 11% of raw protein material (2.8% ofurea), 2.5% of grass material and a maximum of 15% of cellulosicmaterial, 6% of mineral material and 13% moisture correspond to 82forage units per 100 kilos and also contained per 100 kilos 910,000 I.U.of vitamin A, 91,000 I.U. of vitamin D₃, 156 mg of vitamin E and 150 mgof vitamin C. The feed base was prepared from corn, dehydrated alfalfa,wheat stalks, palm oil molasses press cake, urea and mineral vitamincondiment. To form an animal feed, 0.04 kg of an equimolar mixture ofthe A and B isomers of (S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylateor of (S) α-cyano-3-phenoxy-benzyl (1R, trans) 2,2-dimethyl3-(2',2'-dichloro 1',2'-dibromoethyl) cyclopropane-1-carboxylate wasadded to the feed base.

EXAMPLE 53

An antifungal solution was prepared from 50 g of the A and B isomers of(S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'(R,S)-tetrabromoethyl)-cyclopropane-1R-carboxylate,80 g of Emcol H 300 B (mixture of calcium salt of alkyl benzene sulfonicacid and polyoxyethylene ethers) and 870 g of xylene.

An antifungal wettable powder was prepared from 20 g of the A and Bisomers of (S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'(R,S)-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate15 g of Ekapersol S (condensation product of sodium naphthalenesulfonate), 0.5 g of Brecolane NVA (sodium alkyl naphthalene sulfonate),3.95 g of Zeosil 39 (precipitated synthetic hydrated silica) and 25 g ofVercoryl S (colloidal Kaolin).

PESTICIDAL TEST DATA

The following compounds were used in the insecticidal tests: A and Bisomers of (S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate[products Y₁ and Y₂, respectively], the A and B isomers of (S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate[products Y₃ and Y₄, respectively], (R,S) α-cyano-3-phenoxy-benzyl dlcis-trans2,2-dimethyl-3-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1-carboxylate[product Y₅ ], (R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate[product Y₆ ], (R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-)1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate[product Y₇ ], (R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate[product Y₈ ], 5-benzyl-3-furyl-methyl 2,2-dimethyl-3S-(1',2°,2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate [product Y₉ ], (S)α-cyano-3-phenoxy-benzyl (1R, trans)2,2-dimethyl-3-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1-carboxylate[product Y₁₀ ], A isomer or (S) α-cyano-3-phenoxy-benzyl (1R, cis)2,2-dimethyl-3-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1-carboxylate[product Y₁₁ ] and the B isomer of said (1R, cis) compound [product Y₁₂].

A. Lethal activity against household flies

The test insects were 4 days old female houseflies which received atopical application of 1 μl of an acetone solution of the test compoundto the dorsal thorax with the aid of an Arnold micromanipulator. 50insects were used for each test and the number of dead insects after 24hours was determined. The test compounds were used with and without 10parts of piperonyl butoxide synergist per part of test compound. Theresults were expressed in LD₅₀ on the dose in nanograms necessary tokill 50% of the insects and the results are reported in Table I.

                  TABLE I                                                         ______________________________________                                                 LD.sub.50 in ng/insect                                               Compound   with synergist                                                                              without synergist                                    ______________________________________                                        Y.sub.1    0.24          1.13                                                 Y.sub.2    0.55          1.0                                                  Y.sub.3    0.83          1.25                                                 Y.sub.4    0.46          0.60                                                 Y.sub.7    0.99          2.03                                                 Y.sub.10   0.91          5.75                                                 Y.sub.11   0.88          1.67                                                 Y.sub.12   0.82          2.95                                                 ______________________________________                                    

The results of Table I show that the tested compounds have an extremelyelevated lethal activity against the house fly which is even moreelevated with an addition of piperonyl butoxide as a synergist.

B. Lethal activity against larvae of Spodoptera littoralis

The tests were effected by topical application of an acetone solution ofthe test compound with an Arnold micromanipulator to the dorsal thoraxof larvae of Spodoptera littoralis using 10 to 15 larvae for each dose.The larvae were in the 4th stage of larvae development which were about10 days old and were kept at 24° C. and 65% relative humidity. Aftertreatment, the larvae were placed in an artifical nutritive media(Poitoit medium) and the number of dead was determined after 48 hours toascertain the LD₅₀ and the results are reported in Table II.

                  TABLE II                                                        ______________________________________                                        Compound         LD.sub.50 in ng                                              ______________________________________                                        Y.sub.1          0.68                                                         Y.sub.2          0.32                                                         ______________________________________                                    

The results of Table II show that the products had a extremely highlethal activity against the larvae of Spodoptera littoralis.

C. Insecticidal Activity against Spodoptera littoralis caterpillars

The test was effected by topical application of 1μ of an acetonesolution of the test compound to the dorsal thorax of each caterpillarusing 15 individuals of Spodoptera littoralis in the 4th larva stage foreach dose. After treatment, the individuals were placed in an artificalnutritive (Poitoit medium) and the number of dead were determined 24 and48 hours later to ascertain the LD₅₀ dose in ng. The results arereported in Table III.

                  TABLE III                                                       ______________________________________                                        Mg of                         LD.sub.50 after                                 active material               48 Hours                                        per liter in    % efficacity  in                                              Compound                                                                              ng/caterpillar                                                                            24 Hours 48 Hours                                                                             ng/caterpillar                            ______________________________________                                        Equimolar                                                                             0.5         80.0     66.7                                             mixture of                                                                            0.375       53.3     40.0                                             Y.sub.1 and Y.sub.2                                                                   0.25        33.3     33.3   0.38                                              0.125       0        0                                                Equimolar                                                                             0.5         100      100                                              mixture of                                                                            0.375       76.7     73.3                                             Y.sub.3 and Y.sub.4                                                                   0.25        40.0     40.0   0.31                                              0.125       49.3     20.0                                                     2.5                  100                                                      1.25                 66.6                                             Y.sub.7 0.625                53.3   0.51                                              0.312                40.0                                                     1                    93.2                                                     0.75                 66.6                                             Y.sub.9 0.50                 46.6   0.51                                              0.25                 13.3                                             Y.sub.10                            0.22                                      Y.sub.11                            0.57                                      Y.sub.12                            0.65                                      ______________________________________                                    

The results of Table III show that the test compounds had a very highinsecticidal activity against Spodoptera littoralis.

D. Knock Down Activity against House Flies

Female house flies about 4 day old were directly sprayed in a Kearns andMarch chamber with a solution of 1 g/l of the test compound in a 1--1acetone-kerosene mixture using 0.2 ml twice. 50 insects were used foreach test. The readings were effected each minute for 10 minutes andthen at 15 minutes. The KT₅₀ was determined by the usual methods and theresults are reported in Table IV.

                  TABLE IV                                                        ______________________________________                                        Compound         KT.sub.50 in minutes                                         ______________________________________                                        Y.sub.1          3.5                                                          Y.sub.2          6.5                                                          Y.sub.3          4.5                                                          Y.sub.4          4.2                                                          Y.sub.10         6.00                                                         Y.sub.11         6.12                                                         Y.sub.12         6.02                                                         ______________________________________                                    

The KT₅₀ is the time required to knock down 50% of the insects with afixed dose of the tested product as the time is inversely proportionalto the rapid action of the product. The results of Table IV show thatthe tested compounds possess an interesting knock down activity.

E. Insecticidal Activity against Larvae of Epilachna Varivestris

The test was effected by topical application of the test compound as intest C above with penultimate larval stage of Epilachna Varivestris andafter treatment, the larvae were fed bean plants. The number of dead wasdetermined 72 hours after treatment and the results are reported inTable V.

                  TABLE V                                                         ______________________________________                                                  Doses      % of        LD.sub.50 in                                 Compound  in mg/l    Mortality   ng/insect                                    ______________________________________                                                  1.25       100                                                                1          90                                                       Y.sub.3   0.625      60          0.37                                                   0.312      50                                                                 1          90.0                                                               0.625      80.0                                                     Y.sub.4   0.312      70.0        0.20                                                   0.156      40.0                                                               5          100                                                                2.5        80                                                       Y.sub.5   1.25       70          0.53                                                   0.625      50                                                       Y.sub.10                         0.18                                         Y.sub.11                         4.26                                         Y.sub.12                         6.95                                                   2.5        90                                                                 1.25       80                                                       Y.sub.6   0.625      60          0.44                                                   0.312      40                                                                 5          100                                                                2.5        90                                                       Y.sub.7   1.25       50          0.93                                                   0.625      40                                                                 5          100                                                                2.5        80                                                       Y.sub.8   1.25       60          0.88                                                   0.625      40                                                                 0.312      20                                                       ______________________________________                                    

F. Insecticidal Activity against Sitophilus Granarius and TriboliumCastaneum

The test was effected by direct spraying of infested wheat with 5 ml ofan acetone solution of the test product and 0.1 ml of water per 100 g ofwheat contained in a one liter flask in a rotating (movement)evaporator. The wheat was artificially infested with 50 individuals ofeither Sitophilus Granarius or Tribolium Castaneum and the percentage ofdead for each dose was determined after 7 days as compared to untreatedcontrols. The average results for 100 insects was used to determine theLC₅₀ (lethal concentration) which is reported in Table VI.

                  TABLE VI                                                        ______________________________________                                                            %                                                                             efficacity     LC.sub.50                                                                           LC.sub.50                                                in 7 days      in    in                                                       Sito-    Tribo-                                                                              ppm   ppm                                              Doses   philus   lium  for   for                                              in      Grana-   Casta-                                                                              Sito- Tribo-                               Compounds   ppm     rius     neum  philus                                                                              lium                                 ______________________________________                                        Equimolar mix-                                                                            1       67.0     100.0                                            ture of Y.sub.1 and Y.sub.2                                                               0.5     28.7     92.0  0.75  0.32                                             0.25    4.0      24.3                                                         1       62.5     100.0                                            Equimolar mix-                                                                            0.5     18.4     99.0  0.85  0.22                                 ture of Y.sub.3 and Y.sub.4                                                               0.25    2.0      62.6                                                         1.5     90       100                                                          1.0     66.70    96.9                                             Y.sub.10    0.75    35.3     89.5  0.80  0.19                                             0.5     18.2     85.3                                                         0.25    2.0      62.0                                             ______________________________________                                        Natural mortality for Controls:                                                                    Sitophilus 1.0%                                                               Tribolium 4.0%                                           ______________________________________                                    

The results of Table VI show that the tested products have a stronginsecticidal for Tribolium Castaneum and only a slightly lowerinsecticidal activity against Sitophilus Granarius.

G. Insecticidal Activity against Blatella Germanica

The test effected was affected as a film on glass by placing 2 ml of anacetone solution of 10 mg/l of the test product with a Petri dish of 154cm² and then the acetone was evaporated to form a film of 1.3 mg of testcompound per square meter. Adult, male Blatella Germanica were placed onthe film and the number of dead insects was determined after5,10,15,20,25,30,40,50 and 60 minutes. The insects were withdrawn fromthe Petri dish and transferred to a clean wide mouth bottle. The percentof mortality was determined after 24, 48 and 72 hours with respect tothe untreated controls and the results are reported in Table VII.

                                      TABLE VII                                   __________________________________________________________________________              Active                                                                             % Dead (K.D.)              % Mortality                                   Material                                                                           5  10 15 20 25 30 40 50 60 24 48 72                            Compound  in mg/l                                                                            mm mm mm mm mm mm mm mm mm H  H  H                             __________________________________________________________________________    Equimolar mixture                                                                       10   20.0                                                                             40.0                                                                             70.0                                                                             75.0                                                                             80.0                                                                             85.0                                                                             90.0                                                                             100                                                                              100                                                                              95.0                                                                             90.0                                                                             95.0                          of Y.sub.1 and Y.sub.2                                                                  1    15.0                                                                             10.0                                                                             10.0                                                                             20.0                                                                             30.0                                                                             35.0                                                                             60.0                                                                             70.0                                                                             85.0                                                                             40.0                                                                             70.0                                                                             70.0                                    0.1  0  0  0  10.0                                                                             10.0                                                                             10.0                                                                             15.0                                                                             20.0                                                                             30.0                                                                             0  0  0                             Equimolar mixture                                                                       10   30.0                                                                             45.0                                                                             70.0                                                                             85.0                                                                             95.0                                                                             95.0                                                                             100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                           of Y.sub.3 and Y.sub.4                                                                  1     5.0                                                                             10.0                                                                             35.0                                                                             55.0                                                                             60.0                                                                             70.0                                                                             70.0                                                                             95.0                                                                             100                                                                              50.0                                                                             65.0                                                                             65.0                                    0.1  0  0   5.0                                                                              5.0                                                                             10.0                                                                             20.0                                                                             30.0                                                                             30.0                                                                             35.0                                                                             10.0                                                                             10.0                                                                             10.0                          Controls       0  0  0  0  0  0  0  0  0  0  0  0                             __________________________________________________________________________

The results of Table VII show that the test compounds have a remarkableinsecticidal activity against Blatella Germanica.

H. Acaricidal Activity against Tetranychus Urticae

The test was effected on bean leaves infested with 10 female TetranychusUrticae per leaf coated about its periphery with glue. The females wereleft for 24 hours and were then removed and the leaves infested witheggs were divided into 2 groups. The first group was treated with thetest compound by spraying of each leaf with 0.5 ml of an aqueoussolution with a concentration of 50 or 25 g of the test compound perhectare. The second group of leaves were not treated and served as thecontrol. The number of adults living, eggs living, adults and livinglarvae was determined 9 days after the start of the treatment toascertain the percent of mortality of the adults, eggs and larvae withrespect to the controls. The results are reported in Table VIII.

                  TABLE VIII                                                      ______________________________________                                                  Grams of                                                                      active                                                                        Material                                                                             No. of   % Mortality                                         Compound    per ha.  laid eggs                                                                              eggs larvae                                                                              Adults                               ______________________________________                                        Equimolar mix-                                                                            50       103      25.2 33.8                                       ture of Y.sub.1 and Y.sub.2                                                               25       161      22.4 22.4                                       Equimolar mix-                                                                            50        85      45.9 23.9                                       ture of Y.sub.3 and Y.sub.4                                                               25        61      19.7 21.5                                       Y.sub.10    50                                                                            25                54.3 47.6  52.3                                 Control      0       181       7.7  2.4                                       ______________________________________                                    

The results of Table VIII show that the tested products possess an clearacaricidal activity against Tetranychus Urticae.

I. Activity against Panonychus Ulmi

The test was effected with Sirah grape vine with 4 tests for each doseby the block method with untreated control introduced into each blockand each elementary parcel contained 10 vines. A single treatment waseffected with a base of 1000 liters of spraying mixture per hectare witha constant pressure Van de Weij sprayer. The results were determinedafter 7, 16 and 26 days after treatment and the number of moving forms(larvae and adults) on 15 leaves were determined with collection bybrushing and the results are expressed in relation to the untreatedcontrols in Table IX.

                  TABLE IX                                                        ______________________________________                                                     moving form on 15 leaves after days                              Compound                                                                              dose in g/hl                                                                             7         16      26                                       ______________________________________                                        Y.sub.2 2.5        338       453     356                                      Controls                                                                              0          492       967     696                                      ______________________________________                                    

The results of Table IX show that the tested compound has a clearacaricidal activity against adult and larvae Panonychus Ulmi.

J. Hematicidal Activity against Ditylenchus Myceliophagus

The test consisted of placing 0.5 ml of water containing about 2000nematodes into a pill machine containing 10 ml of an aqueous solution ofthe test compound and the degree of mortality was determined with abinocular microscope 24 hours after treatment. 3 tests were madecorresponding each time to a sample of 1 ml of test solution and theresults are reported in Table X.

                  TABLE X                                                         ______________________________________                                                         Active                                                                        Material                                                     Compound         in mg/l    % Mortality                                       ______________________________________                                        Equimolar mixture                                                                              10         99%                                               of Y.sub.1 and Y.sub.2                                                                         1          23.5%                                             Equimolar mixture                                                                              10         99.3%                                             of Y.sub.3 and Y.sub.4                                                                         1          41.5%                                             Controls         0          3.2                                               ______________________________________                                    

The results of Table X show that the tested products have an interestingnematocidal activity against Ditylenchus Myceliophagus.

K. Ixodicide Activity

A solution of 0.5 g of an equimolar mixture of Y₁ and Y₂, 10 g ofpolysorbate 80, 25 g of Triton X 100, 1 g of atocophenol acetate andsufficient ethanol for a final volume of 100 ml was diluted just beforeuse with 50 volumes of water to obtain a concentration of 1/10,000 partsby weight of the active ingredient.

Ticks of Rhipicephalus Sanguineus genus were withdrawn from dogs andwere placed in contact for 30 minutes with the above preparation for anin vitro test. After 30 minutes, it was ascertained that the ticks weredriven to uncoordinated movements and after 4 hours they were dead whilethe control ticks were unaffected.

In a second test, two dogs infested with ixodes of RhipicephalusSanguineus genus were used with the ticks being fixed principally aboutthe head, or the ears, neck and chest. The body of each animal wassoaked with the above solution at a volume of 2.5 liters per dog. Theplace or meeting of the animals was sprayed with the balance of thesolution having served for the treatment. After 24 hours, the ticks werestill fixed and still having movement and after 72 hours, the ticks werestill fixed but dead. The local and general tolerance was excellent whenthe animals were examined 8 days after the treatment.

L. Fungistatic Activity

The fungistatic efficacy of the test product was determined byintroducing 0.5 ml of a solution of the test compound and 0.5 ml of asuspension of spores of the fungus to be combatted adjusted to about100,000 spores per ml into 4 ml of Staron nutritive media and after 7days of incubation, readings were taken by visual observation of thedevelopment of fungus of the absence of development (0 to 100%efficacy). The Staron nutritive media consisted of 20 g of glucose, 6 gof peptone, 1 g of yeast extract, 4 g of corn steep, 0.5 g of sodiumchloride, 1 g of monopotassium phosphate, 0.5 g of magnesium sulfate, 10mg of ferrous sulfate and sufficient water for a final volume of 1liter.

Using the said procedure, equimolar mixtures of compounds Y₁ and Y₂ andcompounds Y₃ and Y₄ showed a fungistatic threshold against FusariumRoseum and Botrytis Cinerea at 25 and 50 ppm, respectively; againstPhoma Species between 25 to 50 and 10 to 25 ppm, respectively and theequimolar mixture of compounds Y₃ and Y₄ showed a fungistatic thresholdagainst Penicillium Rosqueforti between 150 to 200 ppm. The saidmixtures showed interesting antifungal activity in these tests.

M. Insecticidal Activity against Household Flies with FumigantSerpentine

A neutral fumigant serpentine support was impregnated with a solution ofproduct Y₁₀ in acetone and 20 domestic female houseflies 4 to 5 days oldwere released into a closed glass cylinder with a volume of 13.50 dm3.During 2 minutes, the fumigant serpentine was introduced and wasconsumed at one end. The knock down control was effected every minutesand the test was stopped 5 minutes after that the totality of insectswas knocked down. A series of 3 tests was run for each dose and theresults are reported in the following Table.

    ______________________________________                                                Doses in weight                                                                             KT.sub.50 in                                                                              KT.sub.50                                   Compound                                                                              of compound in Coil                                                                         minutes     Average                                     ______________________________________                                                0.4           7.5     8.8   6.6  7.75                                 Y.sub.10                                                                              0.2           11.8    10.2  9.2  10.22                                ______________________________________                                    

Product Y₁₀, when used in fumigant form, has a good insecticidalactivity.

N. Insecticidal Activity against Aedes Aegypti larvae

Wide mouth bottles of 370 ml of volume received 200 ml of water and 1 mlof an acetone solution of product Y₁₀ was added to each. Each bottle wasinfested with 10 larvae of Aedes Aegypti (last larva stage) in 49 ml ofwater. The degree of efficacy was determined 24 to 48 hours after theinfestation and during the test, the bottles were held at 25° in anoven. The LC₅₀ dose was 3.24×10⁻⁵ ppm and shown that product Y₁₀ has astrong insecticidal activity against the larvae of Aedes Aegypti.

O. Activity against Blattella germanica

This test was effected by topical application of 2 microliters ofproduct Y₁₀ in an acetone solution between the second and third pair offeet of adult males of Blattella germanica and the insects were thenkept at 20° C. in a penumbral and were feeded. The test dose were 10,7.5, 5, 3.75 and 2.5 ng/insect and the reading were taken 24 and 48hours and 6 days after the treatment and the LD₅₀ was 1.06 ng per insectwhich indicated a strong insecticidal activity.

P. Activity against Dysdercus fascatus

This test was effected by application of 1 microliter of product Y₁₀ inan acetone solution on the ventral thorax of each individual. The testdoses were 3.75--2.5--1.25--1--0.625 ng/insect and the degree ofefficacy was determined 24 and 48 hours and 5 days after the treatmentand the LD₅₀ was 1.06 ng per insect which indicated a stronginsecticidal activity.

Various modifications of the products and processes of the invention maybe made without departing from the spirit or scope thereof and it is tobe understood that the invention is to be limited only as defined in theappended claims.

We claim:
 1. A compound of the formula ##STR14## wherein X₁ is selectedfrom the group consisting of hydrogen, fluorine, chlorine and bromine,X₂ is selected from the group consisting of fluorine, chlorine andbromine, X₃ is selected from the group consisting of chlorine, bromineand iodine and R is selected from the group consisting of ##STR15## andbenzyl optionally substituted with at least one member of the groupconsisting of alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 6 carbonatoms, alkenyloxy of 2 to 6 carbon atoms, alkadienyl of 4 to 8 carbonatoms, methylenedioxy, benzyl and halogens, R₃ is an aliphatic of 2 to 6carbon atoms having at least one double bond, R₄ is selected from thegroup consisting of hydrogen, --CN and --C|CH, R₅ is selected from thegroup consisting of chlorine and methyl, n is 0,1 or
 2. 2. A compound ofclaim 1 having the 1R, cis or 1R, trans structure.
 3. A compound ofclaim 1 having the dl-cis or dl-trans structure.
 4. A mixture ofcompounds of claim 1 having dl-cis or dl-trans structure.
 5. A compoundof claim 1 wherein X₁ and X₂ are identical and are selected from thegroup consisting of chlorine, bromine and fluorine.
 6. A compound ofclaim 1 wherein X₁ and X₂ are different.
 7. A compound of claim 1wherein R is selected from the group consisting of1-oxo-2-allyl-3-methyl-cyclopent-2-en-4-yl, 3-phenoxy-benzyl, andα-cyano-3-phenoxy-benzyl in racemic or optical isomer form.
 8. Acompound of claim 7 wherein X₁ and X₂ are identical.
 9. A compound ofclaim 1 which is (S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylatein the form of its diastereoisomers with respect to the asymetric carbonatom in the 1'-position or mixtures thereof.
 10. A compound of claim 1in the form of its diastereoisomers with respect to the asymetricalcarbon atom in the 1'-position or mixtures thereof selected from thegroup consisting of(R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate,(R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate,(S) 1-oxo-2-allyl-3-methyl-cyclopent-2-en-4-yl2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate,(S) 1-oxo-2-allyl-3-methyl-cyclopent-2-en-4-yl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate,3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)cyclopropane-1R-carboxylate,(S) 1-oxo-2-allyl-3-methyl-cyclopent-2-en-4-yl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate,(R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate,(S) 1-oxo-2-allyl-3-methyl-cyclopent-2-en-4-yl2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate,(R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate,(S) 1-oxo-2-allyl-3-methyl-cyclopent-2-en-4-yl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylateand (R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate.11. A compound of claim 1 in the form of its diastereoisomers withrespect to the asymetric carbon atom in the 1'-position or mixturesthereof selected from the group consisting of(R,S)α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate,3-phenoxy-benzyl2,2-dimethyl-3R-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylate,3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylate(R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylate,3-phenoxy-benzyl2,2-dimethyl-3S(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylate,(R,S) allethrolone2,2-dimethyl-3S-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylate(R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylate,3-phenoxy-benzyl2,2-dimethyl-3R-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylate(S) allethrolone2,2-dimethyl-3R-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1R-carboxylate(S) allethrolone2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloro-ethyl)-cyclopropane-1R-carboxylate,3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate,(R,S) α-cyano-3-phenoxy-benzyl dl cis trans2,2-dimethyl-3-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1-carboxylate,3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-dichloroethyl)-cyclopropane-1R-carboxylate,(S) allethrolone2,2-dimethyl-3R-(2',2'-dibromo-1',2'-dichloroethyl)-cyclopropane-1R-carboxylate,3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate,3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dichloro-2',2'-dibromoethyl)-cyclopropane-1R-carboxylate,(S) allethrolone2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylate,(R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylate,3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylate,(R,S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3R-(1',2'-dibromo-2',2'-difluoroethyl)-cyclopropane-1R-carboxylateand 3-phenoxy-benzyl2,2-dimethyl-3S-(1',2'-dibromo-2'-chloro-2'-fluoroethyl)-cyclopropane-1R-carboxylate.12. A compound of claim 1 in the form of its diastereoisomers withrespect to the asymetric carbon atom in the 1'-position or mixturesthereof selected from the group consisting of(S)α-cyano-3-phenoxy-benzyl (1R,trans)2,2-dimethyl-3-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1-carboxylate,(S) α-cyano-3-phenoxy-benzyl (1R, cis)2,2-dimethyl-3-(2',2'-dibromo-1',2'-dichloroethyl)-cyclopropane-1-carboxylate,(S) α-cyano-3-phenoxy-benzyl (1R, cis)2,2-dimethyl-3-(1',2',2',2'-tetrachloroethyl)-cyclopropane-1-carboxylateand (R) α-cyano-3-phenoxy-benzyl (1R, trans)2,2-dimethyl-3-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1-carboxylate.13. A compound of claim 1 in the form of its diastereoisomers withrespect to the asymetric carbon atom in the 1'-position or mixturesthereof which is the (S) α-cyano-3-phenoxy-benzyl (1R, trans)2,2-dimethyl-3-(2',2'-dichloro-1',2'-dibromoethyl)-cyclopropane-1-carboxylate.14. A compound of claim 1 in the form of a mixture of cis and transstructures in any proportion.
 15. A compound of claim 14 wherein theproportions by weight are 20/80, 50/50 or 80/20.
 16. A compound of claim1 which is (S) α-cyano-3-phenoxy-benzyl2,2-dimethyl-3S-(1',2',2',2'-tetrabromoethyl)-cyclopropane-1R-carboxylatein the form of its diastereoisomers with respect to the asymetric carbonatom in the 1'-position or mixtures thereof.